AU2018208670A1

AU2018208670A1 - Deuterium-enriched aldehydes

Info

Publication number: AU2018208670A1
Application number: AU2018208670A
Authority: AU
Inventors: Anthony Czarnik
Original assignee: Deuteria Agrochemicals LLC
Current assignee: Deuteria Agrochemicals LLC
Priority date: 2013-03-15
Filing date: 2018-07-25
Publication date: 2018-08-09
Anticipated expiration: 2034-03-15
Also published as: KR20150133758A; JP6670232B2; RU2015141222A; JP2016516727A; WO2014145325A1; CN105101792A; MX2015012802A; EP2975931A1; KR102228670B1; AU2018208670B2; CN110506746A; US9023336B2; AU2014233179B2; US20140271537A1; US20150208651A1; AU2014233179A1; EP2975931A4; BR112015023392A2; US9179670B2

Abstract

Abstract The present invention generally relates to deuterium-enriched aldehydes, compositions comprising deuterium-enriched aldehydes, and methods for slowing the rate of aldehyde autoxidation. In one aspect, the present invention provides a composition comprising a deuterium-enriched aldehyde wherein there are at least 6 x 1 0 A 18 molecules of the aldehyde in the composition, and wherein the aldehyde deuterium isotope is present in the molecule, in an amount greater than 0.10 percent of the aldehydic hydrogen atoms present in the molecule.

Description

The present invention generally relates to deuterium-enriched aldehydes, compositions comprising deuterium-enriched aldehydes, and methods for slowing the rate of aldehyde autoxidation. In one aspect, the present invention provides a composition comprising a deuterium-enriched aldehyde wherein there are at least 6 x 10^Λ18 molecules of the aldehyde in the composition, and wherein the aldehyde deuterium isotope is present in the molecule, in an amount greater than 0.10 percent of the aldehydic hydrogen atoms present in the molecule.

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DEUTERIUM-ENRICHED ALDEHYDES

FIELD OF THE INVENTION [0001] The present invention generally relates to deuterium-enriched aldehydes, compositions comprising deuterium-enriched aldehydes, and methods for slowing the rate of aldehyde autoxidation.

BACKGROUND OF THE INVENTION [0002] Aldehydes are organic compounds containing a H-C(O)- moiety. They are used extensively in industrial processes. Formaldehyde, for instance, is produced on a scale of about 6,000,000 tons/year. Aldehydes are mainly used in the production of resins, but they also find application as precursors to plasticizers and other compounds used in the manufacturing of polymers. On a smaller scale, some aldehydes are used as ingredients in perfumes, flavors and compositions that modulate the behavior of insects, e.g., pheromone containing compositions. [0003] Aldehydes have a tendency to react with atmospheric oxygen to form carboxylic acids (H-C(O)- oxidizes to HO2C-) in a process known as auto-oxidation or autoxidation. The acids produced by autoxidation can lower the quality and usefulness of aldehyde-containing compositions.

[0004] Despite all of the research and development that has been directed to preservation of aldehydes, there is still a need in the art for improved aldehyde-containing compositions and related methods.

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SUMMARY OFTHE INVENTION [0005] In an aspect, the present invention provides a novel deuterium-enriched aldehyde of structure 1:

[0006] In another aspect, the present invention provides a novel method of making a deuteriumenriched aldehyde of structure 1, [0007] In another aspect, the present invention provides a novel composition, comprising: a deuterium-enriched aldehyde of structure 1, [0008] In another aspect, the present invention provides a novel composition, comprising: a deuterium-enriched aldehyde of structure 1 and an organic solvent.

[0009] In another aspect, the present invention provides a novel composition for modulating the behavior of insects, comprising: a deuterium-enriched aldehyde of structure 1 and an optional additional component suitable for the composition.

[0010] In another aspect, the present invention provides a novel method of manufacturing a resin or polymer using a deuterium-enriched aldehyde of structure 1.

[0011] These and other aspects, which will become apparent during the following detailed description, have been achieved by the inventors’ discovery that deuterium can slow the autoxidation of aldehydes.

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BRIEF DESCRIPTION OF THE FIGURES [0012] FIG. 1 shows a graph comparing the amount of air oxidation of benzaldehyde to benzoic acid where the hydrogen atom on the carbonyl group (i.e., H-C(O)Ph) is enriched in its deuterium isotope (/,e., >95% deuterium, “benzaldehyde-D”) and where it is not enriched (i.e., naturally occurring isotopic abundance, “benzaldehyde-H).

[0013] FIG. 2 shows a graph comparing the amount of air oxidation ofhexanal to hexanoic acid where the hydrogen atom of the carbonyl group (i.e., H-C(O)C_SH| i) is enriched in its deuterium isotope (i.e., >95% deuterium, “hexanal-D”) and where it is not enriched (i.e., naturally occurring isotopic abundance, “hexanal-H”).

DETAILED DESCRIPTION OF THE INVENTION [0014] Definitions [0015] All examples provided herein are not intended to be limiting, [0016] “Alkyl” refers to an alkane chemical moiety. The alkanes may be linear, branched, or cyclic. Lower alkyl groups are those that include 1-6 carbon atoms. Higher alkyl groups are those that include 7-20 carbon atoms. Cyclic alkyl or cycloalkyl groups include 3-8 carbon atoms. Examples of such moieties include: CH₃, CH₂CH₃, CH₂CH₂CH₃, CH(CH₃)₂,

CH₂CH₂CH₂CH₃, CH(CH₃)CH₂CH_3l CH₂CH(CH₃)₂, C(CH₃)₃, CH₂CH₂CH₂CH₂CH₃,

CH(CH₃)CH₂CH₂CH₃, CH?CH(CH₃)CH₂CH₃, CH₂CH₂CH(CH₃)₂, ch₂ch₂ch₂ch₂ch₂ch₃, cyclopropyl, cyclobutyl, and cyclopentyl.

[0017] “Substituted alkyl” refers to an alkyl group where one or more of the hydrogen atoms have been replaced with another chemical group. Examples of such other chemical groups include: halo, OH, OR₄ (where R₄ is a lower alkyl group), CF₃, OCF₃, NH₂, NHIG (where R₄ is

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2018208670 25 Jul 2018 a lower alkyl group), NR4R5 (where R4 and R are independently lower alkyl groups), CO JI.

CO2R6 (where IT, is a lower alkyl group), C(O)NH₂, C(O)NHR7 (where R7 is a tower alkyl group), C(O)NR₂Rs (where R7 and Rs are independently lower alkyl groups), CN, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, and substituted heteroaryl.

[0018] “Halo” refers to Cl, F, Br, or I.

[0019] “Alkenyl” refers to a moiety containing only carbon and hydrogen that includes at least one double bond. The alkenes may be linear, branched, or cyclic. Lower alkenyl groups are those that include 2-6 carbon atoms. Higher alkenyl groups are those that include 7-20 carbon atoms. Cyclic alkenyl or cycloalkenyl groups include 5-8 carbon atoms. Examples of such moieties include: CH=CH₂; CH=CHCH₃; C1FCI1=CH; CH=CHCH₂CH₃; CH₂CH=CHCH₃;

CH₂CH₂CH=CH₂; CH=CHCH₂CH₂CH₃; CH=CHCH(CH₃)₂; CH₂CH=CHCH₂CH₃;

CH₂CH₂CH=CHCH₃;CH₂CH₂CH₂CH=CH₂;CH=CHCH₂CH₂CH₂CH₃;CH=CHCH₂CH(CH₃)₂;

cyclopentenyl, and cyclohexenyl, [0020] “Substituted alkenyl” refers to an alkenyl group where one or more of the hydrogen atoms have been replaced with another chemical group. Examples of such other chemical groups include: CO₂H, CO₂R6 (where R_f, is a lower alkyl group), C(O)NH₂, C(O)NHR₇ (where R7 is a lower alkyl group), C(O)NR₂Rs (where R7 and Rs are independently lower alkyl groups),

CN, alkyl, substituted alkyl, alkynyl, substituted alkynyl, aryl, substituted aryl, heteroaryl, and substituted heteroaryl. Where the replaced hydrogen atom is not on the carbon of the double bond, examples of such other chemical groups further include: halo, OH. OCH₃, CF₃, OCF₃,

NH₂, NHR4 (where R4 is a lower alkyl group), and NR4R5 (where R4 and R5 are independently lower alkyl groups).

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2018208670 25 Jul 2018 [0021] “Alkynyl” refers to refers to a moiety containing only carbon and hydrogen that includes a triple bond. The alkynes may be linear or branched. Lower alkynyl groups are those that include 2-6 carbon atoms. Higher alkynyl groups are those that include 7-20 carbon atoms.

Examples of such moieties include: C=CH; C CCI E; CUTCIk CCCIECTE; CI EC CCI b:

(ΊΤ(ΊI-(’ (ΊIu C=CCH₂CH₂CH₃; (ΊEC CCIECIE; CH₂CH₂C=CCH₃; CH₂CH₂CH₂C=CH;

C CCH E'I EC! ECH,: CH₂C=CCH₂CH₂CH₃; CH₂CH₂C=CCH₂CH₃; ClTCITCIECCCIE;

CH₂CH₂CH₂CH₂C=CH; and, C=CCH₂CH(CH₃)₂.

[0022] “Substituted alkynyl” refers to an alkynyl group where one or more of the hydrogen atoms have been replaced with another chemical group. Examples of such other chemical groups include: CO₂H, CCTRf, {where IT, is a lower alkyl group), C(O)NH₂, C(O)NHRy {where Ry is a lower alkyl group), C(O)NR7R₈ (where R₇ and IT are independently lower alkyl groups), CN, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl, substituted aryl, heteroaryl, and substituted heteroaryl. Where the replaced hydrogen atom is not on the carbon of the triple bond,

Examples of such other chemical groups further include: halo, OH, OCH₃, CF₃, OCF₃, NH₂, NHR4 (where R₄ is a lower alkyl group), NR₄R₅ (where R₄ and R5 are independently lower alkyl groups), [0023] “Heteroalkyl” refers to an alkyl group where at least one of the carbon atoms has been replaced with a heteroatom. Examples of heteroatoms include oxygen (“Ό”), nitrogen (“N”) and sulfur (“S”). The heteroalkanes may be linear, branched, or cyclic. Lower heteroalkyl groups are those that include 1 -6 carbons and heteroatoms. Higher heteroalkyl groups are those that include 7-20 carbons and heteroatoms. Examples of heteroalkyl groups include: CH₂OCH₃; CH₂CH₂OCH₃; CH₂N(R₉)CH₃ (where R₉ is a lower alkyl group); CH₂CH₂N(R₉)CH₃ (where R₉

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2018208670 25 Jul 2018 is a lower alkyl group); CI kSCIk; ClkCI LSdC; tetrahydrofuran, tetrahydropyran, and moipholine, [0024] “Substituted heteroalkyl” refers to a heteroalkyl group where one or more of the hydrogen atoms has been replaced with another chemical group. The hydrogen atom that is replaced is typically not on a carbon atom directly attached to the heteroatom. Examples of such other chemical groups include: halo, OH, OCH3, CF3, OCF3, NH₂, NHR₄ (where R₄ is a lower alkyl group), NR4R5 (where R₄ and R? are independently lower alkyl groups), CO₂H, CO2R0 (where R<, is a lower alkyl group), C(O)NH₂, C(O)NHR₇ (where R₇ is a lower alkyl group), C(O)NR₇R_S (where R₇ and R_s are independently lower alkyl groups), CN, alkyl, aryl, and heteroaryl, [0025] “Aryl” refers to an aromatic group containing only carbon and hydrogen (e.g., (<11-. and

CioHe).

[0026] “Substituted aryl” refers to an aryl group where at least one of the hydrogen atoms has been replaced with another chemical group. Examples of such other chemical groups include:

halo, OH, OCH3, CF3, OCF3, NH₂, NHR4 (where R₄ is a lower alkyl group), NR₄R, (where R₄and R5 are independently lower alkyl groups), CO₂H, CO₂Rft (where Re is a lower alkyl group),

C(O)NH₂, C(O)NHR₇ (where R₇ is a lower alkyl group), C(O)NR₇Rjj (where R₇ and Rs are independently lower alkyl groups), CN, alkyl, aryl, and heteroaryl.

[0027] “Heteroaryl” refers to an aromatic group where at least one of the carbon atoms has been replaced by a heteroatom. Examples of such heteroatoms include oxygen (“O”), nitrogen (“N”) and sulfur (“S”). Examples of heteroaryl groups include: C₄H₂O; C4H3N; C₄H₂S; and, C5H4N. [0028] “Substituted heteroaryl” refers to a heteroaryl group where at least one of the hydrogen atoms has been replaced with another chemical group. Examples of such other chemical groups

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[0029] Aspects [0030] In an aspect, the present invention is directed to a deuterium-enriched aldehyde of structure 1:

wherein, R_x is hydrogen, wherein the deuterium isotope is in an amount greater than 0.10 percent of the R_x hydrogen atoms. In certain cases, the deuterium isotope comprises greater than 1% of the R_x hydrogen atoms, or greater than 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%,

90%, or 95% percent of the R_x hydrogen atoms, R[, R₂ and R3 are independently selected from hydrogen (where the hydrogen is un-enriched (i.e., naturally occurring) or is enriched in its deuterium isotope, e.g., more than 1%, 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95%), alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, heteroalkyl, substituted heteroalkyl, aryl, substituted aryl, heteroaryl, and substituted heteroaryl.

Alternatively, the CR1R2R3 moiety forms a group selected from: an aryl, substituted aryl, heteroaryl, and substituted heteroaryl. Alternatively, the CR[R₂ moiety forms a group selected from: an alkenyl and substituted alkenyl. Alternatively, the CR|R₂R₂ moiety forms a group a

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2018208670 25 Jul 2018 group selected from: an alkynyl and substituted alkynyl. Optionally, the aldehyde is substituted with C(O)R_y, wherein R_y is hydrogen, wherein the deuterium isotope is optionally present in an amount greater than 0.10% of the R_y hydrogen atoms, provided that R_x is optionally H when the deuterium isotope is present in an amount greater than 0,10% of the R_y hydrogen atoms. In certain cases, the deuterium isotope comprises greater than 1% of the R_y hydrogen atoms, or greater than 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95% percent of the R_y hydrogen atoms.

[0031] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde of structure 1:

wherein, there are at least 6 x 10¹⁸ molecules of the aldehyde, of structure 1. Compositions of the invention will typically comprise at least 6 x 10¹⁹ molecules, and may, for example, comprise at least 6 x 10 molecules, 6 x 10 molecules, 6 x 10“ molecules, or 6 x 10 molecules. R_x is hydrogen, wherein the deuterium isotope is in an amount greater than 0,10 percent of the R_xhydrogen atoms. In certain cases, the deuterium isotope comprises greater than 1% of the R_xhydrogen atoms, or greater than 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or

95% percent of the R_x hydrogen atoms. R,. R> and R; are independently selected from hydrogen (where the hydrogen is un-enriched (i.e., naturally occurring) or is enriched in its deuterium isotope, e.g., more than 1%, 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or

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95%), alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, heteroalkyl, substituted heteroalkyl, aryl, substituted aryl, heteroaryl, and substituted heteroaryl.

Alternatively, the CR1R2R3 moiety forms a group selected from: an aryl, substituted aryl, heteroaryl, and substituted heteroaryl. Alternatively, the CR1R2 moiety forms a group selected from: an alkenyl and substituted alkenyl. Alternatively, the CR1R2R3 moiety forms a group a group selected from: an alkynyl and substituted alkynyl. Optionally, the aldehyde is substituted with C(O)R_y, wherein R_y is hydrogen, wherein the deuterium isotope is optionally present in an amount greater than 0.10% of the R_y hydrogen atoms, provided that R_x is optionally H when the deuterium isotope is present in an amount greater than 0.10% of the R_y hydrogen atoms. In certain cases, the deuterium isotope comprises greater than 1% of the R_y hydrogen atoms, or greater than 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95% percent of the Ry hydrogen atoms.

[0032] In another aspect, reference to compositions comprising the “aldehyde of structure I”, means compositions comprising at least 0,1 mole of an aldehyde of structure 1, Compositions of the invention may, for example, comprise at least 0.2, 0.5, 1, 2, 3, 4, 5, 10, or 20 moles of an aldehyde of stricture 1.

[0033] In another aspect, reference to compositions comprising the “aldehyde of structure 1”, means compositions comprising at least I gram of an aldehyde of structure I, Compositions of the invention may, for example, comprise at least 5, 10, 20, 30, 40, 50, 100, 500, or 1,000 grams of an aldehyde of structure 1.

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2018208670 25 Jul 2018 [0034] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde of structure 1:

wherein:

there are at least 6 x 10¹⁸ molecules of the aldehyde;

R_x is hydrogen, wherein the deuterium isotope is present in an amount greater than 0.10% of the

R_x hydrogen atoms;

Ri, R2 and R₃ are independently selected from hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, heteroalkyl, substituted heteroalkyl, aryl, substituted aryl, heteroaryl, and substituted heteroaryl;

alternatively, the CR|R₃R₃ moiety forms a group selected from: an aryl, substituted aryl, heteroaryl, and substituted heteroaryl;

alternatively, the CR[R₃ moiety forms a group a group selected from: an alkenyl and substituted alkenyl;

alternatively, the CR1R2R3 moiety forms a group a group selected from: an alkynyl and substituted alkynyl; and, optionally, the aldehyde is substituted with C(O)R_y, wherein R_y is hydrogen, wherein the deuterium isotope is optionally present in an amount greater than 0.10% of the R_y

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[0035] The following are examples of aldehydes according to the present invention:

1. A deuterium-enriched aldehyde of structure 1, where R| and R? are hydrogen, and Ri is a lower alkyl.

2. A deuterium-enriched aldehyde of structure 1, where Rj and R? are hydrogen, and R3 is a higher alkyl.

3. A deuterium-enriched aldehyde of structure 1, where R] and R? are hydrogen, and R3 is a substituted alkyl, where the substituted alkyl is a lower alkyl, and where the one or more other chemical groups are selected from: halo, OH, OR4 (where R4 is a lower alkyl group), CF3, OCF3, NH?, NHR4 (where R4 is a lower alkyl group), \R|R.

(where R4 and R5 are independently lower alkyl groups), CO3H, COiRf, (where R_fl is a lower alkyl group), C(O)NH2, C(O)NHR7 (where R7 is a lower alkyl group), C(O)NR7Rs (where R7 and Rs are independently lower alkyl groups), CN, aryl, substituted aryl, heteroaryl, and substituted heteroaryl.

4. A deuterium-enriched aldehyde of structure 1, where Rj and R? are hydrogen, and R3 is a substituted alkyl, where the substituted alkyl is a higher alkyl, and where the one or more other chemical groups are selected from: halo, OH, OR4 (where R4 is a lower alkyl group), CF3, OCF3, NH2, NHR4 (where R4 is a lower alkyl group), NR4R5 (where R4 and R5 are independently lower alkyl groups), CO?H, CO2R0 (where Rf, is a lower alkyl group), C(O)NH2, C(O)NHRy (where R7 is a lower alkyl group), C(O)NR7R« (where R7 and Rs are independently lower alkyl groups), CN, aryl, substituted aryl, heteroaryl, and substituted heteroaryl.

II

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5. A deuterium-enriched aldehyde of structure 1, where R] and R₂ are hydrogen, and R₃ is a tower alkenyl.

6. A deuterium-enriched aldehyde of structure 1, where R] and R₂ are hydrogen, and R₃is a higher alkenyl,

7. A deuterium-enriched aldehyde of structure 1, where R] and R₂ are hydrogen, and R₃is a substituted alkenyl, where the substituted alkenyl is a lower alkenyl, and where the one or more other chemical groups are selected from: CO₂H, CO₂Re (where Re is a lower alkyl group), C(O)NH₂, C(O)NHR₇ (where R₇ is a lower alkyl group), C(O)NR₇Rs (where R₇ and R_s are independently lower alkyl groups), CN, aryl, substituted aryl, heteroaryl, and substituted heteroaryl.

8. A deuterium-enriched aldehyde of structure 1, where Rj and R₂ are hydrogen, and R₃ is a substituted alkenyl, where the substituted alkenyl is a higher alkenyl, and where the one or more other chemical groups are selected from: CO₂H, CO₂Re (where Ri. is a lower alkyl group), C(O)NH₂, C(O)NHR₇ (where R₇ is a lower alkyl group), C(O)NR₇R₈ (where R₇ and R_s are independently lower alkyl groups), CN, aryl, substituted aryl, heteroaryl, and substituted heteroaryl,

9. A deuterium-enriched aldehyde of structure 1, where R] and R₂ are hydrogen, and R₃ is a tower alkynyl,

10. A deuterium-enriched aldehyde of structure 1, where R] and R₂ are hydrogen, and R₃is a higher alkynyl.

11. A deuterium-enriched aldehyde of structure 1, where R] and R₂ are hydrogen, and R₃is a substituted alkynyl, where the substituted alkynyl is a lower alkynyl, and where the chemical groups are selected from: CO₂H, CO₂Re (where Re is a lower alkyl

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2018208670 25 Jul 2018 group), C(O)NH₂, C(O)NHR7 (where R? is a lower alkyl group), C(O)NRyRii (where R7 and Rs are independently lower alkyl groups), CN, aryl, substituted aryl, heteroaryl, and substituted heteroaryl.

12. A deuterium-enriched aldehyde of structure 1, where R| and R? are hydrogen, and Ri is a substituted alkynyl, where the substituted alkynyl is a higher alkynyl, and where the chemical groups are selected from: COiH. COiRe, (where Rf, is a lower alkyl group), C(O)NH₂, C(O)NHR7 (where R7 is a lower alkyl group), C(O)NR₂Rii (where

R7 and Rs are independently lower alkyl groups), CN, aryl, substituted aryl, heteroaryl, and substituted heteroaryl.

13. A deuterium-enriched aldehyde of structure 1, where R) and R₂ are hydrogen, and R₂ is a lower heteroalkyl.

14. A deuterium-enriched aldehyde of structure 1, where Rj and R₂ are hydrogen, and Ri is a higher heteroalkyl.

15. A deuterium-enriched aldehyde of structure 1, where Rj and R₂ are hydrogen, and Ri is a substituted heteroalkyl, where the substituted heteroalkyl is a lower heteroalkyl.

16. A deuterium-enriched aldehyde of structure 1, where Rj and R₂ are hydrogen, and R₂ is a substituted heteroalkyl, where the substituted heteroalkyl is a higher heteroalkyl.

17. A deuterium-enriched aldehyde of structure 1, where Ri and R₂ are hydrogen, and R₂ is aryl.

18. A deuterium-enriched aldehyde of structure 1, where R| and R? are hydrogen, and R₂ is substituted aryl.

19. A deuterium-enriched aldehyde of structure 1, where Rj and R₂ are hydrogen, and R3 is heteroaryl.

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20. A deuterium-enriched aldehyde of structure 1, where CRJARi is aryl.

21. A deuterium-enriched aldehyde of structure 1, where CR1R2R3 is substituted aryl,

22. A deuterium-enriched aldehyde of structure 1, where CR1R2R3 is heteroaryl.

23. A deuterium-enriched aldehyde of structure 1, where CR1R2R3 is substituted heteroaryl.

24. A deuterium-enriched aldehyde of structure 1, where CR1R2 is alkenyl and R₃ is hydrogen.

25. A deuterium-enriched aldehyde of structure 1, where CR1R2R3 is substituted alkenyl and R₃ is hydrogen.

26. A deuterium-enriched aldehyde of structure 1, where CR1R2 is alkenyl and R₃ is alkyl.

27. A deuterium-enriched aldehyde of structure 1, where CR1R2R3 is substituted alkenyl and R₃ is alkyl.

28. A deuterium-enriched aldehyde of structure 1, where R] is alkyl substituted with

C(O)R_y.

29. A deuterium-enriched aldehyde of structure 1, where Rj is alkyl substituted with

C(O)R_y and R₂ and R₃ are hydrogens.

30. A deuterium-enriched aldehyde of structure 1, where CR1R2R3 aryl substituted with C(O)Ry.

31. A deuterium-enriched aldehyde of structure 1, where CR1R2R3 substituted aryl substituted with C{O)R_y.

[0036] Additional deuterium-enriched aldehydes of the present invention include those numbered 2-64 shown below.

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Rv

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(grandlure IV, E-(3,3-dimethyl)-cyclohexylideneacetaldehyde)

(grandlure III, Z-(3,3-dinietliyl)-cyclohexylideneacetaIdehyde)

Rx (Zll-16:Ald)

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R* (Z9-16:Ald)

Rx (Z9-14:Ald)

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Rx

Rx

(Zll-14:Ald)

Rx (Ell-14:Ald)

R_s

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⁰

(18:Ald)

Rx (E2-9:Ald)

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O

(vanillin)

O-

(14Me-Z8-16:Ald, Z-trogodermal)

Rv

O:

\=/ (R,Z-trogodermal)

ΛΎ7

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(R,E-trogodermal)

R_x

,^RX

O^:

(S_tZ-trogodermal)

(4,8-Me2-10:Ald, tribolure)

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(4R,SR-Me₂-10:Ald, R,R-tribolure) (λ \

R.

(4R_i8S-Me₂-10:Ald, R,S-tribolure)

(grand! u re, E/Z-(3,3-dimethyl)-cyelohexy!ideneacetaldehyde)

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(Z7,Zll,E13-16:Ald)

Rx

(7-heptyloxybutanal).

[0037] Additional deuterium-enriched aldehydes of the present invention include aldehydes 2-64 wherein the deuterium isotope in R_x is in an amount greater than 2% of the hydrogen atoms present in R_K.

[0038] Additional deuteri um-enriched aldehydes of the present invention include aldehydes 2-64 wherein the deuterium isotope in R_x is in an amount greater than 10% of the hydrogen atoms present in R_x.

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2018208670 25 Jul 2018 [0039] Additional deuterium-enriched aldehydes of the present invention include aldehydes 2-64 wherein the deuterium isotope in R_x is in an amount greater than 20% of the hydrogen atoms present in R_x.

[0040] Additional deuterium-enriched aldehydes of the present invention include aldehydes 2-64 wherein the deuterium isotope in R_x is in an amount greater than 30% of the hydrogen atoms present in R_x, [0041] Additional deuterium-enriched aldehydes ofthe present invention include aldehydes 2-64 wherein the deuterium isotope in R_x is in an amount greater than 40% of the hydrogen atoms present in R_x, [0042] Additional deuterium-enriched aldehydes of the present invention include aldehydes 2-64 wherein the deuterium isotope in R_x is in an amount greater than 50% of the hydrogen atoms present in R_x, [0043] Additional deuterium-enriched aldehydes of the present invention include aldehydes 2-64 wherein the deuterium isotope in R_x is in an amount greater than 60% of the hydrogen atoms present in R_x, [0044] Additional deuterium-enriched aldehydes of the present invention include aldehydes 2-64 wherein the deuterium isotope in R_x is in an amount greater than 70% of the hydrogen atoms present in R_x, [0045] Additional deuterium-enriched aldehydes of the present invention include aldehydes 2-64 wherein the deuterium isotope in R_x is in an amount greater than 80% of the hydrogen atoms present in R_x.

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2018208670 25 Jul 2018 [0046] Additional deuterium-enriched aldehydes of the present invention include aldehydes 2-64 wherein the deuterium isotope in R_x is in an amount greater than 90% of the hydrogen atoms present in R_x.

[0047] Additional deuterium-enriched aldehydes of the present invention include aldehydes 2-64 wherein the deuterium isotope in R_x is in an amount greater than 95% of the hydrogen atoms present in R_x, [0048] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64, [0049] Reference to “compositions comprising compounds 2-64” means compositions comprising at least 6 x 10¹⁸ molecules of at least one of aldehydes 2-64, typically at least 6 x 10¹⁹molecules, and may, for example, comprise at least 6 x 10 molecules, 6 x 10 molecules, 6 x 10 molecules, or 6 x 10²³ molecules. R_x is hydrogen, wherein the deuterium isotope is in an amount greater than 0.10 percent of the R_x hydrogen atoms. In certain cases, the deuterium isotope comprises greater than 1 % of the hydrogen atoms, or even greater than 2%, 5%, 10%,

20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95% of the hydrogen atoms.

[0050] In another aspect, reference to “compositions comprising compounds 2-64” means compositions comprising at least 0.1 mole of at least one of aldehydes 2-64. Compositions of the invention may, for example, comprise at least 0.2, 0.5, 1,2, 3, 4, 5, 10, to 20 moles of at least one of compounds 2-64.

[0051] In another aspect, reference to “compositions comprising compounds 2-64” means compositions comprising at least 1 gram of at least one of aldehydes 2-64. Compositions of the invention may, for example, comprise at least 5, 10, 20, 30, 40, 50, 100, 500, to 1,000 grams of at least one of compounds 2-64.

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2018208670 25 Jul 2018 [0052] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64 wherein the deuterium isotope in R_xis in an amount greater than 2% of the hydrogen atoms present in R_x.

[0053] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64 wherein the deuterium isotope in R_xis in an amount greater than 10% of the hydrogen atoms present in R_x.

[0054] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64 wherein the deuterium isotope in R_x is in an amount greater than 20% of the hydrogen atoms present in R_x.

[0055] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64 wherein the deuterium isotope in R, is in an amount greater than 30% of the hydrogen atoms present in R_x, [0056] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64 wherein the deuterium isotope in R_x is in an amount greater than 40% of the hydrogen atoms present in R_x.

[0057] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64 wherein the deuterium isotope in R_xis in an amount greater than 50% of the hydrogen atoms present in R_x.

[0058] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64 wherein the deuterium isotope in R_x is in an amount greater than 60% of the hydrogen atoms present in R_x.

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2018208670 25 Jul 2018 [0059] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64 wherein the deuterium isotope in R_x is in an amount greater than 70% of the hydrogen atoms present in R_x.

[0060] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64 wherein the deuterium isotope in R_xis in an amount greater than 80% of the hydrogen atoms present in R_x.

[0061] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64 wherein the deuterium isotope in R_x is in an amount greater than 90% of the hydrogen atoms present in R_x.

[0062] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 2-64 wherein the deuterium isotope in R, is in an amount greater than 95% of the hydrogen atoms present in R_x, [0063] Additional deuterium-enriched aldehydes of the present invention include aldehydes 65358 listed in the Table A below. For each aldehyde listed in the table, the original aldehyde hydrogen (C(O)-H) has been replaced by R_x (C(O)-R_X). For example, fomnaldehyde-R_x {CHOR_x) is HC(O)-R_X.

Table A

Ex,	Name	Formula
65.	Form aldeh yde-R_x	CHO-R_X
66.	2-Meth yl-2-pro penal- R _x	C₄H₅O-R_x
67.	2-Methylpropanal-R_x	C₄H₇O-R_x
68.	2-Propenal“R_x	C₄H₃O-R_x
69.	2-Butenal-R_x	C₄H₅O-R_x
70.	2-Methyl-2-b utenal-R_x	c₅h₇o-r_x
71.	2-Methylenebutanal-R_x	c₅h₇o-r_x
72.	3-Methyl-2-butenal-R_x	c₅h₇o-r_x
73.	3-Methyl-3-butenal-R_x	c₅h₇o-r_x
74.	3-Meth ylbutanal-R_x	CH>O-R_X
75.	(E)-2-Pentenal-R_x	c₅h₇o-r_x

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76.	2-Methylenepentanal-R_x	C₆H₉O-Rx
77.	2-Pentenal-R_x	CsHyORx
78.	3-Methyl-1 -(vinyloxy)-butane-R_x	CvHnO-Rx
79.	4- Methyl pentanal - R_x	CftHuO-Rx
80.	Furan-2-carbaldehyde-R_x	C^HiO^-Rx
81.	(E)-2-Hexenal-R_x	C6H₉O-R_x
82.	(E)-4-oxo-2-Hexenal-R_x	C₆H₇O₂-R_x
83.	(E,E)-2,4-Dimethyl-2,4-hexadienal-Rx	C₈H\|,O-R_x
84.	(E,E)-2,4-Hexadienal-R_x	C₆H₇O-R_x
85.	(Z)-2-Hexenal-R_x	C₆H₉O-R_x
86.	(Z) -3-Hexenal -R_x	CeH₉O-R_x
87.	(Z)-4-oxo-2-Hexenal-R_x	C₆H₇O₂-R_x
88.	!-Hexenal-R_x	C₆H₉O-R_x
89.	2,3-Dihydroxybenzaldehyde-R_x	C₇H<;Oi-Rx
90.	2-Hexenal-R_x	C6H₉O-Rx
91.	3-((E)-2-Hexenoxy)-hexanal-R_x	C₁₂H₂,O₂-Rx
92.	3,5-Dimethylhexanal-Rx	C₈H₁₅O-R_x
93.	3-EthoxyhexanaER_x	C₈H,₅O2’Rx
94.	3-Hydroxybenzaldehyde-R_x	C₇H,O₂-Rx
95.	3-HydiOxyhexanal-R_x	Ο,ΗπΟΛ
96.	4-Hydroxy-3,5-dimethoxybenzaldehyde-R_K	c₉h₉o₄-r_x
97.	4-Hydroxybenzaldehyde-R_x	CvHA-Rx
98.	5-Methylhexanal-R_x	C₇H_nO-R_x
99.	Hexanal-R_x	CfcHi ,O-R_X
100.	(1R,2S,5S)-Iridodial-R_x	CioHi50₂-R_x
101.	(]R,5S)-6,6-Dimethylbicyclo[3.1 ,l]hept-2-ene-2-carbaldehyde-R_x	C,oH₁₃0-Rx
102.	(!S,2R.3S)-2-( I-Formyl vmy1)-5-methylcyclopentanecarbaldehydeRx	C,₀HbO₂-Rx
103.	(3S,8R)-2-Methyl-5-(1 -formylethyl)-1 -cyclopentene-1carbaldebyde-R_x	CioFIbOi-Rx
104.	(3S,8S)-2-Methyl-5-( 1 -formylethyl)-1 -cyclopentene-1 carbaldehyde-R_x	C₁₀H₁₃O₂-Rx
105.	(5S,8S)-2-Methyl-5-(l-formylethyl)-1-cyclopentene-1carbaldehyde-R_x	C\|oH]₃0₂-R_x
106.	(E)-2-(2-Hydroxyethyl)-6-methyl-2,5-heptadienal-R_x	C₁₀H₁₅O₂-R_x
107.	(E)-2-(2-HydiOxyethylidene)-6-methyl-5-heptenal-R_x	C\|oH₁₅0₂-Rx
108.	(E)-2-Heptenal-R_x	C₇H\| ,O-Rx
109.	(E) -2- Isopropyl-5 - meth y 1 -2-hexen al -R_x	CjoH\|₇0-R_x
110.	(E,Z)-2,4-Heptadienal-R_x	C₇H₉O-R_x
111.	(R)-2-((l R,2R,3S)-3-Methyl-2-vinylcyclopentyl)-propanal-R_x	CuH₁₉O₂-R_x
112.	(R)-2-((lS,2S,3S)-3-Methyl-2-vinylcyclopentyl)-propanal-Rx	ChH₁₉O₂-Rx
113.	(R)-2,6-Dimethyl-5-heptenal-Rx	C₉H\|₅O-R_x
114.	(R)-7-Hydroxy-6,7-dihydro-5H-pyrrolizidine-l-carboxaldehyde-R_x	C₈H«NO₂-R_x
115.	(S)-4-(Prop-1 -en-2-yl)-cyclohex-1 -enecarbaldehyde-R_x	c₁₀h_bo-r_x

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116.	(S)-7 -Hydroxy-6,7-dihydro-5 H-pyrrolizidine-l-carbo xaldehyde-R_x	C₈H₈NO₂-R_x
117.	(Z)-2-Isopropyl-5-methyl-2-hexenal-R_x	c₁₀h₁₇o-r_x
118.	!-Fomiyl-6,7-dihydiO-5H-pyiTolizine-R_x	C₈H₈NO-R_x
119.	l-Formyl-7-hydiOxy-6,7-dihydro-5H-pyiTolizine-R_x	CJbAOAA
120.	2-(3-Methylcyclopentyl)-propanal-R_x	C₉H\|₃O-R_x
121.	2,6-Di meth yl-5-heptenal-R_x	C₉H₁₅O-R_x
122.	2-Acetyl-5-methylcyclopentanecarbaldehyde-R_x	C₉H₁₃O₂-R_x
123.	2-Methoxybenzaldehyde-R_x	C₈H₇O₂-R_x
124.	2-Methyl-l-cyclopentenecarboxaldehyde-R_x	C₇H₉O-R_x
125.	3,3-Dimethyl-5-oxo-7-oxabicyclo[4.1.0]heptane-l-carbaldehyde-R_x	C₉H\| [O₃-R_x
126.	3-Hydroxybenzene-l,2-dicarbaldehyde-R_x	CsH5O₃-R_s
127.	3-Methylbenzaldehyde-R_x	c₈h₇o-r_x
128.	4-(Heptyloxy)-butanal-R_x	C]\|H₂]O₂-R_x
129.	4-Methoxybenzaidehyde-R_x	c₈h₇o₂-r_x
130.	6,7-Dihydro-5 H-pyrrolizine-l-carboxaldehyde-R_x	c₈h₈no-r_x
131.	6.7-Dihydro-7-oxo-5 H-pyrrolizine-l-carbaldehyde-R_x	c₈h₆no₂-r_x
132.	6-Methylheptanal-R_x	c₈h₁₅or_x
133.	7-Hydroxy-6,7-dihydiO-5H-pyiTolizin-1 -carboxaldehyde-R_x	C₈H₈NO₂-R_x
134.	Benzaldehyde-R_x	C₇H₅O-R_x
135.	Cyc lohex anedial-R_x	C₈H_uO₂-R_x
136.	Heptanal-R_x	C₇H₁₃O-R_x
137.	Plagiodial-R_x	C,oHn0₂-R,
138.	(lR,2S)-cis-2-Isopropenyl- l-methylcyclobutaneethanal-R_x	CioH₁₅0-R_x
139.	(1R,2S,5R,8R)-Iridodial-R_x	C,₀Hj₅O₂-R_x
140.	(4S )-(3-Oxo prop-1 -en-2-yl)-cyclohex- l-enecarbaldehyde-R_x	CioHj \|O₂-R_X
141.	(E)-2-(3,3-Dimethylcyclohexylidene)-acetaldehyde-R_x	C,₀H,₅O-R_x
142.	(E)-2-(4-Methyl-3-pentenyl)-butenedial-R_x	C,₀H,₃O₂-Rx
143.	(E)-2-(4-Methyl-3-pentenylidene)-butanedial-R_x	CioHj₃0₂-R_x
144.	(E)-2,7-Octadienal-R_x	C₈H\| [O-R_x
145.	(E)-2-Methyl-5-(3-furyl)-2-pentenal-R_x	CioH]]0₂-R_x
146.	(E)-2-Octenal-R_x	C₈H₁₃O-R_x
147.	(E)-3,7-Dimethyl-2,6-octadienal-R_x	CioH₁₅0-R_x
148.	(E)-3,7-Dimethyl-2,6-octadienal-R_x	C,oH,₅0-R_x
149.	(E)-4-oxo-2-Octenal-R_x	C₈H,\|O₂-R_x
150.	(E)-7-Methyl-2-octen al -R _x	C₉H₁₅O-R_x
151.	(E,E)-2,4-Octadienal-R_x	C₈H„O-Rx
152.	(E,E)-2,6-Dimethyl-8-hydroxy-2,6-octadienal-R_x	CioHi50₂-R_x
153.	(E,E)-2,6-Octadienal-R_x	C₈H,\|O-R_x
154.	(E,E)-2,6-Octadienedial-R_x	C₈H₉O₂-R_x
155.	(E,Z)-2,4-Octadienal-R_x	C₈H_hO-Rx
156.	(E,Z)-2,6-Octadienal-R_x	C₈H„O-Rx
157.	(Z)-2-(3,3-Dimethylcyclohexylidene)-acetaldehyde-R_x	C_J0H₁₅O-Rx
158.	(Z)-3,7 - Dimethyl-2,6 -octadien al -R_x	C₁₀Hi₅O-R_x
159.	(Z,E)-3,7-Dimethyl-2,6-octadienal-R_x	CioHlsO-Rx

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160.	1-Octenal-R_x	C₈Hi₃O-R_x
161.	2-(1-Form ylvinyl)-5-methylcyclopentanecarbaldehyde-R_x	C₁₀H_I3O₂-R_x
162.	2,6,6-Trimethyl-1 -cyclohexene-1 -carbaldehyde~R_x	CioHisO-Rx
163.	2-Ethyloctanal-R_x	CioH\|₉0-R_x
164.	2-Hydroxy-6-methylbenzaldehyde-R_x	C₈H₇O2-R_x
165.	2-Metbyl benzaldehyde-R_x	C₈H₇O-R_x
166.	2-Octenal-R_x	c₈h₁₃or_x
167.	2-Phenyl propenal-R_x	C₉H₇O-R_x
168.	3,7 - Dimethyl-6 -octen al - R_x	C,₀H,₇O-R_x
169.	3-Ethoxy-4-hydroxybenzaldehyde-R_x	C₉H₉O₃-R_x
170.	3-Ethyl benzaldehyde-R_x	C₉H₉O-R_x
171.	3-Isopropyl-6-methyl benzaldehyde-R_x	C„H,₃O-R_x
172.	3-Octenal-R_x	CaHoO-Rx
173.	3-oxo-4-Isopropyl idene-1 -cyclohexene-1 -carboxyaldehyde-R_x	CjoHnOj-Rx
174.	4-Hydroxy-2-methyl benzaldehyde-R_x	C₈H₇O₂-R_x
175.	4-Hydroxy-3-methoxybenzaldehyde-R_x	C₈H₇O₃-R_x
176.	4-Isopropenyl-1 -cyclohexene-1-carbaldehyde-R_x	c₁₀h₁₃o-r_x
177.	4-Isopropenyl-3-oxo-1 -cyclohexene-1 -carboxyaldehyde-R_x	CjoHhOi-Rx
178.	4-oxo-Octenal-R_x	C₈H\| ,(AR_X
179.	4S-4-Isopropenyl-3-oxo-l-cyclohexene-l-carboxyaldehyde-R_x	CioH]jO?-R_x
180.	6,6-Dimethylbicyclo[3.1.1 ]hept-2-ene-2-carbaldehyde-R_x	c₁₀h₁₃o-r_x
181.	7-Methyloctanal-R_x	C₉H\|₇O-R_X
182.	Anisomorphal-R_x	CI0H13O2-R2
183.	cis-2-Isopropenyl-l-methy!cyclobutaneethanal-R_x	CjoHjsO-Rx
184.	Octanal-R_x	C₈H[5O-R_x
185.	Peruphasmal-R_x	CioH₁₃0₂-R_x
186.	(E)-4,8- Nonadienal- R_x	C₉H,₃O-Rx
187.	(E)-8-Methyl-2-nonenal-R_x	CjoHj₇0-R_x
188.	(E,E)-2,4-Nonadienal-R_x	C₉H_l,O-R_x
189.	(Ε,Ε,Ε) -2,4,6- Nonatrienal-R_x	C₉Hi,O-R_x
190.	(E,E,Z)-2,4,6-Nonatrienal-R_x	C₉H_uO-R_x
191.	(E,Z)-2,6-Nonadiena]-R_x	C₉H₁₃O-R_x
192.	(E,Z,Z)-2,4,6-N onatrienal-R_x	C₉HuO-R_x
193.	(Z)-3-Nonenal-R_x	C₉Hl5O-R_x
194.	(Z)-4,8-Nonadienal-R_x	c₉h₁₃o-r_x
195.	(Z)-4-Nonenal-R_x	C₉H₁₅O-R_x
196.	(Z)-8-Methyl-2-nonenal-R_x	CioHnO-Rx
197.	2-Phenyl-2-butenal-R_x	CjoH₉0-R_x
198.	3-(4-Methoxyphenyl)-2-propenal-R_x	CjoH₉02-R_x
199.	3-Phenyl-2-propenal-R_x	C₉H₇O-R_x
200.	3-Phenyl propanal-R_x	C₉H₉O-R_x
201.	6-Ethyl benzaldehyde-R_x	C₉H₉O-R_x
202.	8-Meth ylnonanal-R _x	CjoHj₉0-R_x
203.	9-Acetyloxynonanal-R_x	ChH]₉O₃-R_x

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204.	Nonanal-R_x	c₉h,₇o-r_x
205.	(E)-2,9-Decadienal-R_x	c₁₀h₁₅o-r_x
206.	(E)-2-Decenal-R_x	CioHnO-R,
207.	{E)-4-oxo-2-Decenal-R_x	CioH_J50₂-R_x
208.	(E)-8-Hydroxy-4,8-dimethyl-4,9-decadienal-R_x	C,₂H₁₉O₂-R_x
209.	(E)-9-Methyl-2-decenal-R_x	C]]H_!9O-R_x
210.	(E,E)-2,4-Decadienal-R_x	c₁₀h₁₅o-r_x
211.	(E,Z)-2,4-Decadienal-R_x	CioHisO-Rx
212.	{Z)-4-Decenal-R_x	C,₀H,₇O-R_x
213.	(Z)-5-Decenal-R_x	CjoHj70-R_x
214.	(Z)-9-Methyl-2-decenal-R_x	C]jHii)O-R_x
215.	1-Decenal-R_x	C₁₀H₁₇O-R_x
216.	2-Decenal-R_x	Ci₀H₁₇O-R_x
217.	2-Ethyldecanal-R_x	Cj₂H₂₃O-R_x
218.	Decanal-R_x	CioHi(jO-R_x
219.	(5E)-2,6,10-Trimethyiundeca-5,9-dienal-R_x	C]4H₂₃O-R_X
220.	(E)-2-Undecenal-R_x	C„H₁₉O-R_x
221.	(E)-6-Ethyl-2,10-dimethyl-5,9-undecadienal-R_x	c₁₅h₂₅o-r_x
222.	10-Urtdecenal-R_x	C„H,₉O-R_x
223.	2-Butyl-2-octenal-R_x	Ci₂H₂,O-R_x
224.	5-Methyl-2-phenyl-2-hexenal-R_x	c₁₃h₁₅o-r_x
225.	8-Isopropyl-5-methyl-3,4,4a,5,6,7,8,8a-octahydronaphthalene-2carbaldehyde-R_x	C₁₅HnO-R_x
226.	syn-4,6-Dimethylundecanal-R_x	C]₃H₂5O-R_x
227.	Undecan al-R_x	CiiH₂]O-R_x
228.	(3R,5R,9R)-3,5,9-Trimethyldodecanal-R_x	C₁₅H₂₉O-R_x
229.	(3S,6E)-7-Ethyl-3,11 -dimethyldodeca-6,10-dienal-R_x	C\|6H₂₇O-R_x
230.	(9R)-3,5,9 -Trimeth y!dodecanal-R_x	Cj5H₂₉O-R_x
231.	(E)-10-Dodecenal-R_x	Ci₂H₂jO-R_x
232.	(E)-2-Dodecenal-R_x	Cj₂H₂]O-R_x
233.	(E)-3,7,l l-Trimethyl-6,10-dodecadienal-R_x	Ci₅H₂₅O-R_x
234.	(E)-6-Dodecenal-R_x	C₁₂H₂iO-R_x
235.	(E)-7-Dodecenal - R_x	C\|₂H₂\|O-R_x
236.	(E)-8-Dodecenal-R_x	Ci₂H₂,O-R_x
237.	(E)-9,11-Dodecadienal-R_x	C_i2H_i9O-R_x
238.	{E)-9-Dodecenal-R_x	C₁₂H₂₁O-R_x
239.	(E,E)-3,7,11 -Tri methyl-2,6,10-dodecatrienal-R_x	C\|₅H₂₃O-R_x
240.	(E,E)-7-Ethyl-3,11-dimethyl-2,6,10-dodecatrienal-R_x	Cji,H₂5O-R_x
241.	(E,E)-8,10-Dodecadienal-R_x	Ci₂Hi₉O-R_x
242.	(E,E,E)-3,7-Dimethyl-8,1 l-dioxo-2,6,9-dodecatrienal-R_x	C₁₄H₁₇O3-R_x
243.	(E.E.Zjrii^-Dinnethyl-S. 11 -dioxo-2,6,9-dodecatrienal-R_x	C,4H₎₇O₃-R_x
244.	(E,Z)-5,7-Dodecadienal-R_x	C]₂H]₉O-R_x
245.	(E,Z)-7,9-Dodecadienal-R_x	Ci₂Hjt)O-R_x
246.	(E,Z)-8,10- Dodecadienal-R_x	C₁₂H₁₉O-R_X

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247.	(S,E)-3,7,ll-Trimethyl-6,10-dodecadienal-R_x	C_i5H₂₅O-R_x
248.	(Z)-2-Methyl-5-(( 1 R,5R,6S)-2,6-dimethylbicyc)o[3.1,1 ]hept-2-en6-yl)-pent-2-enal-R_x	C\|₅H₂₁O-R_X
249.	(Z)-5 -Dodecenal - R_x	C\|₂H₂₎O-R_x
250.	(Z)-7-Dodecenal-R_x	C\|₂H₂₎O-R_x
251.	(Z)-9,11 -Dodecadienal-R_x	Ci₂H]()O-R_x
252.	(Z)-9-Dodecenal~R_x	Ci₂H₂,O-R_x
253.	(Z,E)-3,7,1 i -Tri methyl-2,6,10-dodecatrienal-R_x	C,₅H₂₃O-R_x
254.	(Z,E)-5,7-Dodecadienal-R_x	Cj₂Hj₉O-R_x
255.	(Z,E)-7-Ethyl-3,11-dimethyl-2,6,10-dodecatrienal-R_x	Ci₆H₂₅O-R_x
256.	(Z,E)-8,10-Dodecadienal-R_x	Ci₂Hj₉O-R_x
257.	(Z,Z)-5,7-Dodecadienal-R_x	C₁₂H₁₉O-R_x
258.	2-Ethyldodecana]-R_x	C_J4H₂₇O-R_x
259.	3,7,11 -Tri methy 1 - (E)-6,1O-dodecadienal -R_x	C₁₅H₂₅O-R_x
260.	Dodecanal-R_x	Ci₂H₂₃O-R_x
261.	syn-4,6-Dimethyldodecanal-R_x	C_]4H₂₇O-R_x
262.	(3S,4R,6E, 10Z)-3,4,7,11 -Tetramethyl-6,1O-tridecadienal-R_x	C₁₇H₂₉O-R_x
263.	(Z)-4-T ridecenal-R_x	C_J3H₂₃O-R_x
264.	13-Acetyloxytridecanal-R_x	Ci5H₂₇O₂-R_x
265.	Tridecan al-R_x	Ci₃H₂₃O-R_x
266.	(E)-l 1,13-Tetradecadienal-R_x	CmH^O-R,
267.	(E,E)-8,I0-Tetradecadienal-R_x	C_i4H_2iO-R_x
268.	(E,Z)-4,9-Tetradecadienal-R_x	C]₄H₂₄O-R_X
269.	(Z)-l l,13-Tetradecadienal-R_x	C_!4H₂₂O-R_x
270.	(Z) -5-Tetradecenal-R_x	Ci₄H₂₃O-R_x
271.	(Z)-7-Tetradecenal-R_x	C₁₄H₂₅O-R_x
272.	{Z)-9,13-Tetradecadien-l 1 -ynal-R_x	C\|₄H₁₉O-R_x
273.	(Z,E)-9,12-Tetradecadienal-R_x	C,₄H₂₃O-R_x
274.	(Z,Z)-8,10-Tetradecadienal-R_x	Ci₄H₂iO-R_x
275.	(Z,Z)-9,11-Tetradecadienal-R_x	C₁₄H₂₃O-R_x
276.	10,12~Tetradecadienal-R_x	C\|₄H₂₃O-R_x
277.	2-Ethyltetradecanal~R_x	C,₆H₃iO-R_x
278.	3-oxo-13-Tetradecenal-R_x	C,₄H₂₁O₂-R_x
279.	3-oxo-Tetradecanal-R_x	C j₄H₂₃O₂-R_x
280.	5,8-Tetradecadienal-R_x	Ci₄H₂₃O-R_x
281.	5-Tetradecenal-R_x	C₁₄H₂₅O-R_x
282.	(E)-5,9-Dimethyl-2-(6-methylhept-5-en-2-yl)-deca-4,8-dienal-R_x	c₂₀h„o-r_x
283.	(E,Z)-9,11-Pentadecadienal-R_x	C)5H₂5O-R_x
284.	(Z)-1O-Pentadecenal-R_x	Ci5H₂₇O-R_x
285.	(Z)-6,14-Pentadecadienal-R_x	Ci₃H₂₅O-R_x
286.	(Z,Z)-9,11-Pentadecadienal-Rx	CisH^O-Rx
287.	2-Hexyl-2-decenal-R_x	C_]6H₂₉O-R_x
288.	Pentadecanal-R_x	Ci5H₂₉O-R_x
289.	(1R)-Pimaral-R_x	C₂qH₂₉O-R_x

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290.	(E)-10- Hexadecenal-R_x	CisHjtjO-Rx
291.	(E)-l 1-Hexadecenal-R_x	C₁₆H₂,jO-R_x
292.	(E,E)-10,14-Hexadecadienal-R_x	C\|6H₃₇O-R_X
293.	(E,E)-1 l,13-Hexadecadienal-R_x	C₁₆H₂₇OR_x
294.	(E,E)-9,11-Hexadecadienal-R_x	CifiH^vO-Rx
295.	(Ε,Ε,Ε)-ΙΟ. J 2,14-Hexadecatrienal-R_x	C]r,H₂₃O-R_x
296.	(E,E,E)-3,7,11,15-tetiamethyl-2,6,10,14-hexadecatetraenal-R_x	C₂₀H₃₁O-R_x
297.	(Ε,Ε,Ζ)-10, J 2 J 4-Hexadecatrienal-R_x	C_i;>ll_?,OR_x
298.	(E,E,Z)-4,6,11 -Hexadecatrienal-R_x	c,₆h₂₅o-r_x
299.	(E,E,Z,Z)-4,6,11,13-Hexadecatetraenal-R_x	Ci6H₃₃O-R_x
300.	(E,Z)-10,12-Hexadecadienal-R_x	Ci₆H₂₇O-R_x
301.	(E,Z)-J l,13-Hexadecadienal-R_x	C₁₆H₂₇O-R_x
302.	{E,Z)-4,6-Hexadecadienal-R_x	C\|6H₂₇O-R_x
303.	(E,Z)-6,11-Hexadecadienal-R_x	C,₆H₂₇O-R_x
304.	(E,Z)-8,11-Hexadecadienal-R_x	Ci6H₂₇O-R_x
305.	(E,Z)-9,11-Hexadecadienal-R_x	Ck,H₂₇O-R_x
306.	(Z)-10-Hexadecenal-R_x	Ck,H₂₉O-R_x
307.	(Z)-12-HexadecenaER_x	C,₆H₂₉O-R_x
308.	(Z)-13-Hexadecen-ll-ynal-R_x	C_!6H₂₅O-R_x
309.	(Z)-3-oxo-9-Hexadecenal-R_x	Ci6H₂₇O₂-R_x
310.	(Z,E)-10,12-Hexadecadienal-R_x	C₁₆H₂₇O-R_x
311.	(Z,E)-1 l,13-Hexadecadienal-R_x	c₁₆h₂₇o-r_x
312.	(Z,E)-7,11-Hexadecadienal-R_x	C\|₆H₂₇O-R_x
313.	(Z,E)-9,11-Hexadecadienal-R_x	Cjf,H₂₇O-R_x
314.	(Z,Z)-10,12-Hexadecadienal-R_x	Ck,H₂₇O-R_x
315.	(Z,Z)-1 l,13-Hexadecadienal-R_x	c₁₆h₂₇o-r_x
316.	(Z,Z)-9,11-Hexadecadienal-R_x	C\|₆H₂₇O-R_x
317.	11-Hexadecynal-R_x	c_]6h₂₇o-r_x
318.	2-Methylhexadecanal - R_x	Cj₇H₃₃O-R_x
319.	7-Hexadecenal-R_x	Ci6H₂₉O-R_x
320.	9-HexadecenaLR_x	c₁₆h_2(J0-r_x
321.	(Z)-9- Heptadecenal-R_x	C,₇H₃iO-R_x
322.	1 -Heptadecenal-R_x	c₁₇h₃,o-r_x
323.	2-Heptadecenal-R_x	c₁₇h₃₁o-r_x
324.	Heptadecanal-R_x	C]₇H₃₃O-R_x
325.	(E)-l l-Octadecenal-R_x	C₁₈H₃₃O-R_x
326.	(E)-13-0ctadecenal-R_x	C₎₈H₃₃O-R_x
327.	(E)-14- Octadecenal-R_x	C,₈H₃₃O-R_x
328.	(E)-2-0ctadecenal- R_x	C₁₈H₃₃O-R_x
329.	{E,E)-1 l,14-0ctadecadienal-R_x	c₁₈h₃₁o-r_x
330.	(E,Z)-2,13-Octadecadienal-R_x	C\|₈H₃₎O-R_x
331.	(E,Z)-3,13-0ctadecadienal-R_x	C\|₈H₃jO-R_x
332.	(Z)-l 1-Octadecenal-R_x	Cj₈H₃₃O-R_x
333.	(Z)-13-0ctadecenal-R_x	Ci₈H₃₃O-R_x

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334.	(Z)-9-Octadecenal-R_x	C₁₈H₃₃O-R_X
335.	(Z,Z)-1 l,13-Octadecadienal-R_x	C_i8H₃₁O-R_x
336.	(Ζ,Ζ)-13,15-Octadecadienal-Rx	CisHjjiO-Rx
337.	(Z,Z)-3,13-Octadecadienal-R_x	C₁₈H₃₁O-R_X
338.	(Z,Z)-9,12-Octadecadienal-R_x	Ci₈H₃]O-R_x
339.	(Z,Z,Z)-9,12,15-Octadecatrienal-R_x	Ci₈H₂₉O-R_x
340.	! -Octadecenal-R_x	Ci₈H₃₃O-R_x
341.	9-Octadecenal-R_x	C₁₈H₃₃O-R_x
342.	Octadecanal-R_x	C,₈H₃₅O-R_x
343.	(Z)-10-N onadecenal-R_x	C]₉H₃5O-R_x
344.	(Z)-9-Nonadecenal-R_x	C₁₉H₃₅O-R_x
345.	(Z)l 1-Eicosenal-R_x	c₂₀h₃₇o-r_x
346.	!2-Deacetoxy-12-oxo-scalaiadial-R_x	C25H₃₅O₃-R_x
347.	1-Eicosenal-R_x	c₂₀h₃₇o-r_x
348.	Deacetylscalaradial-R_x	C₂iH₃₇O₃-R_x
349.	Eicosanal-R_x	C₂oH₃₉0-R_x
350.	Scalaradial-R_x	C₂₇H₃₉O₄-R_x
351.	Docosanal-R_x	C₂₂H₄₃O-R_x
352.	Tetracosanal-R_x	C₂₄H₄₇O-R_x
353.	Pentacosanal-R_x	c₂sl I₄₉()-R_x
354.	Hexacosanal-R_x	C₂₆H₅₁O-R_x
355.	Heptacosanal-R_x	C₂₇H₅₃O-R_x
356.	Octacosanal-R_x	C₂₈H₅5O-R_x
357.	Triacontanal-R_x	C₃oH5₉0-R_x
358.	Dotriacontanal-R_x	C₃₂H6₃O-R_x

[0064] Additional deuterium-enriched aldehydes of the present invention include aldehydes 65358 listed in the Tables B-L below.

[0065] Table B: Examples 64-358 of Table A, except that the deuterium isotope in R_x is in an amount greater than 2% of the hydrogen atoms present in R_x.

[0066] Table C: Examples 64-358 of Table A, except that the deuterium isotope in R_x is in an amount greater than 10% of the hydrogen atoms present in R_x.

[0067] Table D: Examples 64-358 of Table A, except that the deuterium isotope in R_x is in an amount greater than 20% of the hydrogen atoms present in R_v

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2018208670 25 Jul 2018 [0068] Table E: Examples 64-358 of Table A, except that the deuterium isotope in R_x is in an amount greater than 30% of the hydrogen atoms present in R_x, [0069] Table F: Examples 64-358 of Table A, except that the deuterium isotope in R_x is in an amount greater than 40% of the hydrogen atoms present in R_x.

[0070] Table G: Examples 64-358 of Table A, except that the deuterium isotope in R_x is in an amount greater than 50% of the hydrogen atoms present in R_x.

[0071] Table H: Examples 64-358 of Table A, except that the deuterium isotope in R_x is in an amount greater than 60% of the hydrogen atoms present in R_x, [0072] Table I: Examples 64-358 of Table A, except that the deuterium isotope in R_x is in an amount greater than 70% of the hydrogen atoms present in R_x.

[0073] Table J: Examples 64-358 of Table A, except that the deuterium isotope in R_x is in an amount greater than 80% of the hydrogen atoms present in R_x, [0074] Table K: Examples 64-358 of Table A, except that the deuterium isotope in R_x is in an amount greater than 90% of the hydrogen atoms present in R_x.

[0075] Table L: Examples 64-358 of Table A, except that the deuterium isotope in R_x is in an amount greater than 95% of the hydrogen atoms present in R_x, [0076] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358 of Table A, [0077] Reference to “compositions comprising compounds 65-358” means compositions comprising at least 6x10 molecules of at least one of aldehydes 65-358, typically at least 6 x 10¹⁹ molecules, and may, for example, comprise at least 6 x 10° molecules, 6 x 10“' molecules, x 10 molecules, or 6 x 10²³ molecules. R_x is hydrogen, wherein the deuterium isotope is in an amount greater than 0.10 percent of the R_x hydrogen atoms. In certain cases, the deuterium

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2018208670 25 Jul 2018 isotope comprises greater than 1% of the hydrogen atoms, or even greater than 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95% of the hydrogen atoms, [0078] In another aspect, reference to “compositions comprising compounds 65-358” means compositions comprising at least 0,1 mole of at least one of aldehydes 65-358. Compositions of the invention may, for example, comprise at least 0,2, 0,5, 1, 2, 3, 4, 5, 10, to 20 moles of at least one of compounds 65-358.

[0079] In another aspect, reference to “compositions comprising compounds 65-358” means compositions comprising at least I gram of at least one of aldehydes 65-358. Compositions of the invention may, for example, comprise at least 5, 10, 20, 30, 40, 50, 100, 500, to 1,000 grams of at least one of compounds 65-358.

[0080] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358 of Table B.

[0081] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358 of Table C, [0082] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358 of Table D.

[0083] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358 of Table E, [0084] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358 of Table F, [0085] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358 of Table G.

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2018208670 25 Jul 2018 [0086] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358 of Table H, [0087] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358 of Table I.

[0088] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358 of Table J.

[0089] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358 of Table K, [0090] In another aspect, the present invention provides a composition, comprising: a deuterium-enriched aldehyde selected from aldehydes 65-358 of Table L.

[0091] Compounds of the present invention are more stable to autoxidation than the corresponding aldehydes where the hydrogen atom attached to the carbonyl moiety (i.e., HC(O)) is not enriched in the deuterium isotope. For instance, where the deuterium isotope comprises greater than 90 percent of the subject hydrogen atoms, the rate of autoxidation - i.e., conversion of the aldehyde to its corresponding carboxylic acid through oxidation by atmospheric oxidation in the absence of an oxidation catalyst (e.g., metal or transition metalbased catalyst) - is reduced by at least 10 percent (e.g., if 10.0 percent of the aldehyde without deuterium enrichment experiences autoxidation, less than 9.0 percent of the aldehyde with deuterium enrichment experiences autoxidation under the same conditions). In certain cases, the rate is reduced by at least 20 percent, 30 percent, 40 percent, 50 percent, 60 percent, 70 percent, percent or 90 percent.

[0092] Compounds 1-358 can be synthesized using any appropriate method. Examples of such methods include: reduction of the cones ponding acid halide with deuterium gas (see USP

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5,149,820); reduction of the corresponding tertiary amide using CpzZriDjCl (see Georg et al.

Tet. Lett. 2004; 45: 2787-2789); and, reduction of the corresponding ester using L1AID4 to produce an alcohol and subsequent oxidation (see Kim et al., J. Label Compd Radiopharm 2004;

47: 921-934)(or just oxidation of a corresponding alcohol);

[0093] Alternatively, an additional method includes reduction of the un-enriched aldehyde with NaBD₄ or NaCNBD₃ followed by re-oxidation with pyridinium chlorochromate or another suitable oxidant, in which the deuterium enrichment of the aldehyde is a result of the isotope effect, [0094] In another aspect, the present invention provides compositions comprising one or more of aldehydes 1-64 and an organic solvent (e.g., an alcohol (e.g., ethyl alcohol and isopropyl alcohol), ether (e.g., dimethyl ethyl), or alkane (e.g., hexanes)). In another aspect, the organic solvent is ethyl alcohol. Examples of the concentration of the ethyl alcohol include 50-97.5 weight percent, 60-97 weight percent, and 70-96 weight percent.

[0095] In another aspect, the present invention provides compositions comprising one or more of aldehydes 65-358 and an organic solvent (e.g., an alcohol (e.g., ethyl alcohol and isopropyl alcohol), ether (e.g., dimethyl ethyl), or alkane (e.g., hexanes)). In another aspect, the organic solvent is ethyl alcohol. Examples of the concentration of the ethyl alcohol include 50-97.5 weight percent, 60-97 weight percent, and 70-96 weight percent, [0096] In another aspect, the compositions of the present invention comprise an additional ingredient. Examples of additional ingredients include: dipropylene glycol; isopropyl myristate;

oils (e.g., coconut oil); and liquid waxes (e.g., jojoba oil).

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2018208670 25 Jul 2018 [0097] The compositions discussed herein also can be used, for example, in a perfume. Reference to “perfume” means a mixture comprising fragrant compounds and solvents used to give the human body, animals, objects and living spaces a pleasant scent.

[0098] In another aspect, the present invention provides novel compositions for modulating the behavior of insects (e.g., attracting or inhibiting insect species), comprising: a deuteriumenriched aldehyde selected from structures 1-64, wherein the aldehyde is a pheromone and an optional additional component or components suitable for the composition (e.g., a pesticide, dispensing material or device, solvent, adhesive capable of trapping the insect, etc,).

[0099] In another aspect, the present invention provides novel compositions for modulating the behavior of insects (e.g., attracting or inhibiting insect species), comprising: a deuteriumenriched aldehyde selected from structures 65-358, wherein the aldehyde is a pheromone and an optional additional component or components suitable for the composition (e.g., a pesticide, dispensing material or device, solvent, adhesive capable of trapping the insect, etc.).

[00100] In another aspect, the composition comprises a pheromone blend.

[00101] A pheromone blend, comprises: at least one pheromone aldehyde selected from the deuterium-enriched aldehydes of the present invention and at least one additional pheromone that is either an un-enriched aldehyde or a different pheromone aldehyde selected from the deuterium-enriched aldehydes of the present invention.

[00102] In another aspect, the present invention provides novel methods for modulating the behavior of insects (e.£., attracting insect species or inhibiting the mating or aggregation of insect species), comprising:

a. applying a deuterium-enriched aldehyde pheromone of the present invention. Or a composition comprising a deuterium-enriched aldehyde pheromone of the present

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2018208670 25 Jul 2018 invention and a optionally a solvent or other additional component suitable for the composition, to a surface of an object (e.g., a lure within a trap wherein the insect enters but cannot leave, a lure or trap wherein the insect sticks to a surface of the trap, or a lure or trap containing a chemical capable of killing the insect); and,

b. placing the object in a location where one desires either to attract insect species or inhibiting the mating or aggregation of insect species.

[00103] In another aspect, a pheromone blend is applied (either neat or as a part of a composition of the present invention), [00104] In another aspect, two or more deuterium-enriched aldehyde pheromones of the present invention are applied (either neat or as a part of a composition ofthe present invention).

[00105] Alternatively, the method comprises: distributing a composition comprising a deuterium-enriched aldehyde pheromone of the present invention into an area (e.g,, by aerial spraying over crops), into a stored product (e.g., traps or disruptant dispensers in grain crops), onto vegetation (e.g., by manual application of dollops of an emulsion (e.g., SPLAT® type formulation) onto plants, vines, leaves, or shoots), or by applying by aerial dissemination or manual placement a composition of pheromone-impregnated chips, pheromone containing polymer hollow fibers, or pheromone containing rubber septa, in order to modulate the behavior of insects by disruption of mating behavior. More than one composition or method may be combined to achieve the desired reduction of crop damage.

[00106] In another aspect, a pheromone blend is present in the distributed composition.

[00107] In another aspect, two or more deuterium-enriched aldehyde pheromones of the present invention are present in the distributed composition.

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2018208670 25 Jul 2018 [00108] In another aspect, the deuterium-enriched aldehyde pheromone of the present invention is distributed impregnated on a chip, in a polymer hollow fiber, or adsorbed within a rubber septum.

[00109] In another aspect, a pheromone blend is distributed impregnated on a chip, in a polymer hollow fiber, or adsorbed within a rubber septum.

[00110] In another aspect, two or more deuterium-enriched aldehyde pheromones of the present invention are distributed impregnated on a chip, in a polymer hollow fiber, or adsorbed within a rubber septum, [00111] The modulation of insect behavior can comprise attraction to an aldehyde pheromone trap, or alternatively, disruption of mate-finding and mating behavior, A benefit of such insect behavior modulation can be diminished crop damage, such as reducing damage to fruits, nuts, seeds, grains, grapes, leaves, shoots, bark, grain, or other valuable crops by reducing insect damage to said crop, whether in the field or in storage after harvesting said valuable crop.

[00112] In another aspect, the modulating composition of the present invention, comprises: a deuterium-enriched aldehyde pheromone of the present invention formulated to be used in an attractant trap (an attractant composition), [00113] In another aspect, the modulating composition of the present invention, comprises: a pheromone blend formulated to be used in an attractant trap (an attractant composition).

[00114] In another aspect, two or more deuterium-enriched aldehyde pheromones of the present invention are present in the modulating composition.

[00115] In another aspect, the present invention provides a method of using an attractant composition in an attractant trap.

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2018208670 25 Jul 2018 [00116] In another aspect, the present invention provides a method of using a deuteriumenriched aldehyde pheromone as a component of a composition to attract, trap, or monitor adult insects in a stored product with the goal of minimizing crop product infestation and loss. In another aspect, a pheromone blend is in the composition. In another aspect, two or more deuterium-enriched aldehyde pheromones of the present invention are present in the composition.

[00117] In another aspect, the modulating composition of the present invention, comprises a deuterium-enriched aldehyde pheromone of the present invention formulated to be used as a mating disruptant (a disruptant composition). A disruptant composition is typically dispersed throughout part or all of an area to be protected, [00118] In another aspect, a pheromone blend is present in the disruptant composition.

[00119] In another aspect, two or more deuterium-enriched aldehyde pheromones of the present invention are present in the disruptant composition.

[00120] In another aspect, the present invention provides a method of using a disruptant composition in an area to be protected (e.g., a crop field). It will be understood by those skilled in the art that dismption of mating by adult insects will reduce the population of offspring.

Frequently it is the offspring, or larvae, of the species that are responsible for damage to the field crop or harvested crop product, A skilled person will understand that disruption of mating may be an indirect method of reducing damage to field crops or harvested crop products by larval forms of the insects that feed on the crop or crop product.

[00121] In another aspect, the disruptant composition is made using an oil/water emulsion preparation to deposit the disruptant onto a carrier. Examples of carriers include a polymeric hollow loop, a rubber (e.g., septum) or polymeric earner, and impregnable chips.

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2018208670 25 Jul 2018 [00122] Examples of types of attractant and/or disruptant formulations include: microencapsulation, hollow tube dispensers, bait stations, oil-water emulsions, and other volatile deuterium-enriched aldehyde dispensers.

[00123] Microencapsulation refers to encapsulating at least one deuterium-enriched aldehyde pheromone of the present invention in a polymer. The polymer is selected to delay the release of the pheromone for at least a few days. The microencapsulated pheromone(s) can be applied by spraying.

[00124] Examples of hollow tube dispensers include plastic twist-tie type dispensers, plastic hollow fibers, and plastic hollow microfibers. These types of dispensers are filled with at least one disruptant or a disruptant composition of the present invention and then distributed throughout the area to be protected.

[00125] Bait stations are stationary devices that are typically used to attract and kill.

Examples include platforms comprising at least pheromone aldehyde of the present invention and a glue board (or some other mechanism capable of trapping the attracted insect). Instead of or in addition to glue, the station can contain a pesticide that negatively affects the insect (e.g., reduces its ability to mate or reproduce), [00126] Dispensers or high-emission dispensers are devices that either passively or actively release a pheromone aldehyde of the present invention. Examples of passive release include pheromone sachets or an emulsion (e.g., a SPLAT® (Specialized Lure And Pheromone Technology) formulation). Active dispensers may release bursts of at least one pheromone aldehyde of the present invention (or composition containing at least one pheromone aldehyde of the present invention) at timed intervals or by continuous release through volatilization from the dispenser.

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2018208670 25 Jul 2018 [00127] As used herein, a pheromone is a deuterium-enriched aldehyde of structure 1 that has the traits of a natural pheromone, i,e., a chemical capable communicating with at least one insect species. Pheromones may act as alarm signals, provide trails to food sources, attract parasitoids or other predators, and/or attract insects of the same species for the purpose of mating.

[00128] Unless otherwise specified, when a pheromone is recited in the present invention it can be a single deuterium-enriched aldehyde of structure 1 or a blend of pheromones wherein at least one is a deuterium-enriched aldehyde of structure 1. The second, third, fourth, fifth, or more pheromone can be a deuterium-enriched aldehyde of structure 1 or a non-deuteriumenriched aldehyde [00129] In another aspect, a composition of the present invention, comprises: 2, 3,4, 5, 6, 7, 8, 9, or 10 deuterium-enriched aldehyde pheromones of the present invention, [00130] In another aspect, a composition of the present invention, comprises: 2 or more deuterium-enriched aldehyde pheromones of the present invention.

[00131] In another aspect, a composition of the present invention, comprises: 3 or more deuterium-enriched aldehyde pheromones of the present invention, [00132] In another aspect, a composition of the present invention, comprises: 4 or more deuterium-enriched aldehyde pheromones of the present invention, [00133] In another aspect, a composition of the present invention, comprises: 5 or more deuterium-enriched aldehyde pheromones of the present invention.

[00134] In another aspect, a composition of the present invention, comprises: at least 1, 2,

3, 4, Or 5 deuterium-enriched aldehyde pheromones of the present invention and at least 1, 2, 3,

4, or 5 un-enrichedun-enriched pheromones.

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2018208670 25 Jul 2018 [00135] In another aspect, a composition of the present invention, comprises: at least 1 deuterium-enriched aldehyde pheromone of the present invention and at least 1 un-enriched pheromone.

[00136] In another aspect, a composition of the present invention, comprises: at least 2 deuterium-enriched aldehyde pheromones of the present invention and at least 1 un-enriched pheromone.

[00137] In another aspect, a composition of the present invention, comprises: at least 1 deuterium-enriched aldehyde pheromones of the present invention and at least 2 un-enriched pheromones.

[00138] In another aspect, a composition of the present invention, comprises: at least 3 deuterium-enriched aldehyde pheromones of the present invention and at least 1 un-enriched pheromone, [00139] In another aspect, a composition of the present invention, comprises: at least 3 deuterium-enriched aldehyde pheromones of the present invention and at least 2 un-enriched pheromones.

[00140] In another aspect, a composition of the present invention, comprises: at least 3 deuterium-enriched aldehyde pheromones of the present invention and at least 3 un-enriched pheromones.

[00141] Examples of insects for which a deuterium-enriched pheromone (or pheromones) can be prepared include: corn earworm (Heliothis (Helicoverpa) zea), tobacco budworm (Heliothis virescens), cotton bollworm (Heliothis (Helicoverpa) armigera), horse chestnut leaf miner (Cameraria orhidella), eastern spruce budworm (Chorisioneura fumiferana), rice borer (Chilo suppressalis), grain weevils (Trogoderma spp.), grain/flower weevils (Triholium spp.),

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2018208670 25 Jul 2018 cotton boll weevil (Anthonomus grandis), citrus leaf miner (Phvllocnistis citrella), carob moth (Ectomyelois ceratoniae), and Asian longhorn beetle (Atioplophom glabripetinis), among many others. A complete listing of aldehyde pheromones of insects and the target species using the pheromones is available on the Pherobase.com data base and is hereby incorporated in totality into this application (http://www.pheiObase.com/database/compound/compounds-aldes.php). One or more of the known aldehydic pheromones for these insects can be replaced by a deuterium-enriched aldehyde of the present invention.

[00142] For example, a pheromone composition for the corn earworm containing Z1116:Ald can be replaced with compound 27 of the present invention. Representative examples of such deuterium-enriched aldehyde pheromones include compounds selected from: aldehydes 8,

15, 23, 24, 27, 28, 29, 30,34, 35,36, 37,38, 39,40, 41,42, 43,44, 45, 46, 47,48, 49, 50, 51,52,

53,54, 55,56, 57,58, 59,60, 61,62, 63, and 64.

[00143] In another aspect, the present invention provides novel compositions for modulating the behavior of insects, comprising: at least one deuterium-enriched aldehyde that is a pheromone, wherein the deuterium-enriched aldehyde is selected from: aldehydes 27, 28, and

35.

[00144] In another aspect, the present invention provides novel compositions for modulating the behavior of insects, comprising: at least one deuterium-enriched aldehyde that is a pheromone, wherein the deuterium-enriched aldehyde is selected from: aldehydes 27 and 28. [00145] In another aspect, the present invention provides novel compositions for modulating the behavior of insects, comprising: at least one deuterium-enriched aldehyde that is a pheromone, wherein the deuterium-enriched aldehyde is: aldehyde 36,

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2018208670 25 Jul 2018 [00146] In another aspect, the present invention provides novel compositions for modulating the behavior of insects, comprising: at least one deuterium-enriched aldehyde that is a pheromone, wherein the deuterium-enriched aldehyde is selected from: aldehydes 37 and 38. [00147] In another aspect, the present invention provides novel compositions for modulating the behavior of insects, comprising: at least one deuterium-enriched aldehyde that is a pheromone, wherein the deuterium-enriched aldehyde is selected from: aldehydes 27, 28. and

44.

[00148] In another aspect, the present invention provides novel compositions for modulating the behavior of insects, comprising: at least one deuterium-enriched aldehyde that Is a pheromone, wherein the deuterium-enriched aldehyde is: aldehyde 49.

[00149] In another aspect, the present invention provides novel compositions for modulating the behavior of insects, comprising: at least one deuterium-enriched aldehyde that is a pheromone, wherein the deuterium-enriched aldehyde is: aldehyde 55.

[00150] In another aspect, the present invention provides novel compositions for modulating the behavior of insects, comprising: at least one deuterium-enriched aldehyde that is a pheromone, wherein the deuterium-enriched aldehyde is: aldehyde 59.

[00151] In another aspect, the present invention provides novel compositions for modulating the behavior of insects, comprising: at least one deuterium-enriched aldehyde that is a pheromone, wherein the deuterium-enriched aldehyde is selected from: aldehyde 40, 60, and

61.

[00152] In another aspect, the present invention provides novel compositions for modulating the behavior of insects, comprising: at least one deuterium-enriched aldehyde that is a pheromone, wherein the deuterium-enriched aldehyde is: aldehyde 62.

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2018208670 25 Jul 2018 [00153] In another aspect, the present invention provides novel compositions for modulating the behavior of insects, comprising: at least one deuterium-enriched aldehyde that is a pheromone, wherein the deuterium-enriched aldehyde is: aldehyde 64.

[00154] Compounds of the present invention are also more stable to autoxidation than their corresponding non-deuterium enriched counterpails when included in compositions of the present invention. The rate of auto oxidation is reduced by at least 10 percent. In certain cases, the rate is reduced by at least 20 percent, 30 percent, 40 percent, 50 percent, 60 percent, 70 percent, 80 percent or 90 percent, [00155] The skilled person will recognize that pheromones or pheromone blends for a given species may include non-aldehyde components, such as an alkyl, alkenyl, alkynyl alcohol or an alkyl, alkenyl or alkynyl ester. When the blend for optimal attraction includes such an additional non-aldehyde component, the skilled person would augment the deuterium-labeled pheromone of the present invention with the additional attractant or disruptant compound that increases the efficacy of modulation of the insect behavior, e.g., mating disruption or attraction to a trap.

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2018208670 25 Jul 2018

wherein:

there are at least 6x10 molecules of the aldehyde present in the composition;

R_x is hydrogen, wherein the deuterium isotope is present in an amount greater than 0.10% of the R_x hydrogen atoms;

unless otherwise defined, R|, R₂ and R₃ are independently selected from hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, heteroalkyl, substituted heteroalkyl, aryl, substituted aryl, heteroaryl, and substituted heteroaryl; alternatively, the CRjR₃R₃ moiety forms a group selected from: an aryl, substituted aryl, heteroaryl, and substituted heteroaryl;

alternatively, the CR|R₂ moiety forms a group a group selected from: an alkenyl and substituted alkenyl;

alternatively, the CRiR₂R₃ moiety forms a group a group selected from: an alkynyl and substituted alkynyl; and, optionally, the aldehyde is substituted with C(O)R_y, wherein R_x is hydrogen, wherein the deuterium isotope is present in an amount greater than 0.10% of the R_y hydrogen atoms.

[00157] Table 1:

Structure #

Solvent (weight%)

Ex.#

Ri, R2, R

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A.	1	As defined	Ethyl alcohol 70-96% by weight
B.	1	one of Ri, R₂ and Iff is alkyl	Ethyl alcohol 70-96% by weight
C.	1	one of Rj, R₂ and R_i is substituted alkyl	Ethyl alcohol 70-96% by weight
D.	1	one of Rj, R₂ and R₂ is alkenyl	Ethyl alcohol 70-96% by weight
E.	1	one of R[, R₂ and Iff is substituted alkenyl	Ethyl alcohol 70-96% by weight
F.	1	one of R\|, R₂ and R₂ is alkynyl	Ethyl alcohol 70-96% by weight
G.	1	one of R], R₂ and R₂ is substituted alkynyl	Ethyl alcohol 70-96% by weight
H.	1	one of Rj, R₂ and R₃ is heteroalkyl	Ethyl alcohol 70-96% by weight
I.	1	one of Ri, R₂ and Iff is substituted heteroalkyl	Ethyl alcohol 70-96% by weight
J.	1	one of R,, R₂ and R₂ is aryl	Ethyl alcohol 70-96% by weight
K.	1	one of R\|, R₂ and R₂ is substituted aryl	Ethyl alcohol 70-96% by weight
L.	1	one of Rj, R₂ and R₂ is heteroaryl	Ethyl alcohol 70-96% by weight
M.	1	one of R[, R₂ and R3 is substituted heteroaryl	Ethyl alcohol 70-96% by weight
N.	1	one of R\|, R₂ and R₂ is alkyl and another is hydrogen	Ethyl alcohol 70-96% by weight
0.	1	one of Rj, R₂ and R₂ is substituted alkyl and another is hydrogen	Ethyl alcohol 70-96% by weight
P.	1	one of Rj, R₂ and R₂ is alkenyl and another is hydrogen	Ethyl alcohol 70-96% by weight
Q.	1	one of Ri, R₂ and R3 is substituted alkenyl and another is hydrogen	Ethyl alcohol 70-96% by weight
R.	1	one of Ri, R₂ and R3 is alkynyl and another is hydrogen	Ethyl alcohol 70-96% by weight
S.	1	one of Ri, R₂ and R₂ is substituted	Ethyl alcohol

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		alkynyl and another is hydrogen	70-96% by weight
T.	1	one of R], R₂ and R₂ is heteroalkyl and another is hydrogen	Ethyl alcohol 70-96% by weight
u.	1	one of Rj, R₂ and R> is substituted heteroalkyl and another is hydrogen	Ethyl alcohol 70-96% by weight
V.	1	one of Ri, R₂ and R₂ is aryl and another is hydrogen	Ethyl alcohol 70-96% by weight
w.	1	one of R\|, R₂ and R₂ is substituted aryl and another is hydrogen	Ethyl alcohol 70-96% by weight
X.	1	one of R\|, R₂ and R₂ is heteroaryl and another is hydrogen	Ethyl alcohol 70-96% by weight
Y.	1	one of Rj, R₂ and R₂ is substituted heteroaryl and another is hydrogen	Ethyl alcohol 70-96% by weight
z.	1	Ri, R₂ and R, is alkyl and the other two are hydrogen	Ethyl alcohol 70-96% by weight
AA.	1	one of R\|, R₂ and R₂ is substituted alkyl and the other two are hydrogen	Ethyl alcohol 70-96% by weight
BB.	1	one of Rj, R₂ and Ri is alkenyl and the other two are hydrogen	Ethyl alcohol 70-96% by weight
CC.	1	one of Rj, R₂ and R₃ is substituted alkenyl and the other two are hydrogen	Ethyl alcohol 70-96% by weight
DD.	1	one of Rj, R₂ and R3 is alkynyl and the other two are hydrogen	Ethyl alcohol 70-96% by weight
EE.	1	one of Rj, R₂ and R₂ is substituted alkynyl and the other two are hydrogen	Ethyl alcohol 70-96% by weight
FF.	1	one of Rj, R₂ and R₂ is heteroalkyl and the other two are hydrogen	Ethyl alcohol 70-96% by weight
GG.	1	one of Rj, R₂ and R₃ is substituted heteroalkyl and the other two are hydrogen	Ethyl alcohol 70-96% by weight
HH.	1	one of Ri, R₂ and IT is aryl and the other two hydrogen	Ethyl alcohol 70-96% by weight
II.	1	one of R[, R₂ and R3 is substituted aryl the other two are hydrogen	Ethyl alcohol 70-96% by weight
JJ.	1	one of R1, R₂ and R₂ is heteroaryl and the other two are hydrogen	Ethyl alcohol 70-96% by weight
KK.	1	one of R], R₂ and R₂ is substituted heteroaryl and the other two are	Ethyl alcohol

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		hydrogen	70-96% by weight
LL.	1	CR1R2R3 is aryl	Ethyl alcohol 70-96% by weight
MM.	1	CRjRiRi is substituted aryl	Ethyl alcohol 70-96% by weight
NN.	1	CR1R2R3 is heteroaryl	Ethyl alcohol 70-96% by weight
OO.	1	CR1R2R3 is substituted heteroaryl	Ethyl alcohol 70-96% by weight
PP.	1	CR\|Ri alkenyl and Ri is hydrogen	Ethyl alcohol 70-96% by weight
QQ.	1	CR]R₂ substituted alkenyl and R3 is hydrogen	Ethyl alcohol 70-96% by weight
RR.	1	CR1R2 alkenyl and R3 is alkyl	Ethyl alcohol 70-96% by weight
SS.	1	CR1R2 substituted alkenyl and R; is alkyl	Ethyl alcohol 70-96% by weight
TT.	1	R] is alkyl substituted with C(O)R_y	Ethyl alcohol 70-96% by weight
UU.	1	R] is alkyl substituted with C(O)R_y and Ri and R-, are hydrogens	Ethyl alcohol 70-96% by weight
vv.	1	CR1R2R3 is aryl substituted with C(O)R_y	Ethyl alcohol 70-96% by weight
ww.	1	CR]R₂R3 is substituted aryl substituted with C(O)R_y	Ethyl alcohol 70-96% by weight
XX.	2		Ethyl alcohol 70-96% by weight
YY.	3	-	Ethyl alcohol 70-96% by weight
zz.	4	-	Ethyl alcohol 70-96% by weight
AAA.	5	-	Ethyl alcohol 70-96% by weight
BBB.	6	-	Ethyl alcohol 70-96% by weight

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ccc.	7	-	Ethyl alcohol 70-96% by weight
DDD.	8	-	Ethyl alcohol 70-96% by weight
EEE.	9	-	Ethyl alcohol 70-96% by weight
FFF.	10	-	Ethyl alcohol 70-96% by weight
GGG.	11	-	Ethyl alcohol 70-96% by weight
HHH.	12	-	Ethyl alcohol 70-96% by weight
III.	13	-	Ethyl alcohol 70-96% by weight
JJJ.	14	-	Ethyl alcohol 70-96% by weight
KKK.	15	-	Ethyl alcohol 70-96% by weight
LLL.	16	-	Ethyl alcohol 70-96% by weight
MMM.	17	-	Ethyl alcohol 70-96% by weight
NNN.	18	-	Ethyl alcohol 70-96% by weight
000.	19	-	Ethyl alcohol 70-96% by weight
PPP.	20	-	Ethyl alcohol 70-96% by weight
QQQ-	21	-	Ethyl alcohol 70-96% by weight
RRR.	22	-	Ethyl alcohol

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			70-96% by weight
sss.	23	-	Ethyl alcohol 70-96% by weight
TTT.	24	-	Ethyl alcohol 70-96% by weight
uuu.	25	-	Ethyl alcohol 70-96% by weight
vvv.	26	-	Ethyl alcohol 70-96% by weight
WWW.	27	-	Ethyl alcohol 70-96% by weight
XXX.	28	-	Ethyl alcohol 70-96% by weight
YYY.	29	-	Ethyl alcohol 70-96% by weight
zzz.	30	*	Ethyl alcohol 70-96% by weight
AAAA.	31	-	Ethyl alcohol 70-96% by weight
BBBB.	32	-	Ethyl alcohol 70-96% by weight
CCCC.	33	-	Ethyl alcohol 70-96% by weight
DDDD.	34	-	Ethyl alcohol 70-96% by weight
EEEE.	35	-	Ethyl alcohol 70-96% by weight
FFFF.	36	-	Ethyl alcohol 70-96% by weight
GGGG.	37	-	Ethyl alcohol 70-96% by weight

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HHHH.	38	-	Ethyl alcohol 70-96% by weight
IIII.	39	-	Ethyl alcohol 70-96% by weight
JJJJ.	40	-	Ethyl alcohol 70-96% by weight
KKKK.	41	-	Ethyl alcohol 70-96% by weight
LLLL.	42	-	Ethyl alcohol 70-96% by weight
MMMM.	43	-	Ethyl alcohol 70-96% by weight
NNNN.	44	-	Ethyl alcoho) 70-96% by weight
0000.	45	-	Ethyl alcohol 70-96% by weight
PPPP.	46	-	Ethyl alcohol 70-96% by weight
QQQQ.	47	-	Ethyl alcohol 70-96% by weight
RRRR,	48	-	Ethyl alcohol 70-96% by weight
SSSS.	49	-	Ethyl alcohol 70-96% by weight
tttt.	50	-	Ethyl alcohol 70-96% by weight
UUUU.	51	-	Ethyl alcohol 70-96% by weight
VVVV.	52	-	Ethyl alcohol 70-96% by weight
WWWW.	53	-	Ethyl alcoho)

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			70-96% by weight
xxxx.	54	-	Ethyl alcohol 70-96% by weight
YYYY.	55	-	Ethyl alcohol 70-96% by weight
//././.	56	-	Ethyl alcohol 70-96% by weight
AAAAA.	57	-	Ethyl alcohol 70-96% by weight
BBBBB.	58	-	Ethyl alcohol 70-96% by weight
CCCCC.	59	-	Ethyl alcohol 70-96% by weight
DDDDD.	60	-	Ethyl alcohol 70-96% by weight
EEEEE.	61	*	Ethyl alcohol 70-96% by weight
FFFFF.	62	-	Ethyl alcohol 70-96% by weight
GGGGG.	63	-	Ethyl alcohol 70-96% by weight
HHHHH.	64	-	Ethyl alcohol 70-96% by weight

[00158] Table 2: Examples A-HHHHH of Table 2 correspond to examples A-HHHHH of Table 1, except that the deuterium isotope in R_x is in an amount greater than 2% of the hydrogen atoms present in R_x, [00159] Table 3: Examples A-HHHHH of Table 2 correspond to examples A-HHHHH of Table 1, except that the deuterium isotope in R_x is in an amount greater than 10% of the hydrogen atoms present in R_x.

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2018208670 25 Jul 2018 [00160] Table 4: Examples A-HHHHH of Table 2 correspond to examples A-HHHHH of Table 1, except that the deuterium isotope in R_x is in an amount greater than 50% of the hydrogen atoms present in R_x.

[00161] Table 5: Examples A-HHHHH of Table 2 correspond to examples A-HHHHH of Table 1, except that the deuterium isotope in R_x is in an amount greater than 90% of the hydrogen atoms present in R_x.

[00162] In another aspect, compounds according to the present invention can be used to make resins and/or polymers. The method comprises the steps of: mixing a deuterium-enriched aldehyde selected from structures 1-64 with an aromatic compound (i.e., aryl-containing compound) or an olefinic compound (i.e., alkenyl-containing compound) in a solvent and in the presence of a catalyst, in such a way as to initiate a reaction between the aromatic or olefinic compound and the aldehyde; and, isolating the reaction product (e.g., resin or polymer) resulting from the reaction. The catalyst may be a Bronsted acid (e.g., aqueous sulfuric or hydrochloric acid), a Lewis acid (e.g., AlCfi), a base (e.g., KOH) or a metal (e.g., transition metal). The reaction may be earned out at room temperature or at elevated temperature (e.g., 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 110 °C or 120 °C), The reaction may also be carried out at atmospheric pressure or at elevated pressure (e.g., 2 atm, 3 atm, 4 atm or 5 atm).

[00163] In another aspect, compounds according to the present invention can be used to make resins and/or polymers. The method comprises the steps of: mixing a deuterium-enriched aldehyde selected from structures 65-358 with an aromatic compound (i.e., aryl-containing compound) or an olefinic compound (i.e., alkenyl-containing compound) in a solvent and in the presence of a catalyst, in such a way as to initiate a reaction between the aromatic or olefinic compound and the aldehyde; and, isolating the reaction product (e.g., resin or polymer) resulting

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2018208670 25 Jul 2018 from the reaction. The catalyst may be a Bronsted acid (e.g., aqueous sulfuric or hydrochloric acid), a Lewis acid (e.g., A1C1₃), a base (e.g., KOH) or a metal (e.g., transition metal). The reaction may be carried out at room temperature or at elevated temperature (e.g., 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 110 °C or 120 °C), The reaction may also be carried out at atmospheric pressure or at elevated pressure (e.g., 2 atm, 3 atm, 4 atm or 5 atm).

[00164] The rate of autoxidation of aldehydes in the polymerization/resin producing reaction is reduced by at least 10 percent as compared to use of non-deuterium enriched aldehydes under the same conditions. In certain cases, the rate is reduced by at least 20 percent, percent, 40 percent, 50 percent, 60 percent, 70 percent, 80 percent or 90 percent.

[00165] The following general methods of making a resin and/or polymer are meant to illustrate, not limit, the present invention.

[00166] General Method 1 [00167] An aromatic compound (e.g., naphthalene, benzene, substituted benzene such as toluene) is heated in an acidic mixture (e.g., sulfuric acid and water) for 6 horn’s at 160 °C. The mixture is cooled to 100 °C, and a deuterium-enriched aldehyde selected from structures 1-64 is added in an amount that is less than a molar equivalent of the aromatic compound. The resulting mixture is kept at 100 °C at a time period ranging from 30 minutes to 16 hours to afford a condensation polymer, [00168] General Method IA [00169] An aromatic compound (e.g., naphthalene, benzene, substituted benzene such as toluene) is heated in an acidic mixture (e.g., sulfuric acid and water) for6 hours at 160 °C. The mixture is cooled to 100 °C, and a deuterium-enriched aldehyde selected from structures 65-358 is added in an amount that is less than a molar equivalent of the aromatic compound. The

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2018208670 25 Jul 2018 resulting mixture is kept at 100 °C at a time period ranging from 30 minutes to 16 hours to afford a condensation polymer, [00170] General Method 2 [00171] To a mixture of a deuterium-enriched aldehydes selected from structures 1-64 and an aromatic alcohol (e.g., resorcinol) at room temperature is added an acidic solution (e.g., aqueous HCI), This affords a condensation polymer upon isolation, [00172] General Method 2B [00173] To a mixture of a deuterium-enriched aldehydes selected from stiuctures 65-358 and an aromatic alcohol (e.g., resorcinol) at room temperature is added an acidic solution (e.g., aqueous HCI), This affords a condensation polymer upon isolation, [00174] General Method 3 [00175] To an aromatic alcohol (e.g., phenol, resorcinol) in an organic solvent (e.g., ether such as dioxane) is slowly added acid (e.g., sulfuric acid). A deuterium-enriched aldehyde selected from structures 1-64 is added dropwise with stirring. The reaction mixture is heated and the contents refluxed for 2 hours. The organic solvent and water are removed, and the reaction mixture is cooled. Precipitation of material provides the condensation polymer, [00176] General Method 3A [00177] To an aromatic alcohol (e.g., phenol, resorcinol) in an organic solvent (e.g., ether such as dioxane) is slowly added acid (e.g., sulfuric acid). A deuterium-enriched aldehyde selected from structures 65-358 is added dropwise with stirring. The reaction mixture is heated and the contents refluxed for 2 hours. The organic solvent and water are removed, and the reaction mixture is cooled. Precipitation of material provides the condensation polymer, [00178] General procedure for measurement of aldehyde oxidations

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Claims

WHAT IS CLAIMED IS:

1. A composition, comprising: a deuterium-enriched aldehyde of structure 1:

2018208670 25 Jul 2018 wherein:

there are at least 6 x 10¹⁸ molecules of the aldehyde in the composition;

R_x is hydrogen, wherein the deuterium isotope is present in an amount greater than 0.10% of the

R_x hydrogen atoms;

Rj, R₂ and R₃ are independently selected from hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, heteroalkyl, substituted heteroalkyl, aryl, substituted aryl, heteroaryl, and substituted heteroaryl;

alternatively, the CR|R₂R₃ moiety ton ns a group selected from: an aryl, substituted aryl, heteroaryl, and substituted heteroaryl;

alternatively, the CR[R₂ moiety forms a group a group selected from: an alkenyl and substituted alkenyl;

alternatively, the CR[R₂R₃ moiety forms a group a group selected from: an alkynyl and substituted alkynyl; and, optionally, the aldehyde is substituted with C(O)R_y, wherein R_y is hydrogen, wherein the deuterium isotope is optionally present in an amount greater than 0.10% of the R_y

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2, The composition according to claim 1, wherein the deuterium-enriched aldehyde is selected from aldehydes 2-64:

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A

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3, The composition according to claim 1, wherein the deuterium-enriched aldehyde is selected from aldehydes 65-358:

Ex. Name 65. Formaldehyde-R_x 66. 2-Methyl-2-pro penal-R_x 67. 2-Methylpropanal-R_x 68. 2-Propenal-R_x 69. 2-Butenal-R_x 70. 2-Methyl-2-butenal-R_x 71. 2-Methylenebutanal-R_x 72. 3-Methyl-2-butenal-R_x 73. 3-Methyl-3-butenal-R_x 74. 3-Methylbutanal-R_x 75. (E)-2~Pentenal-R_x 76. 2-Methylenepentanal-R_x 77. 2-Pentenal-R_x 78. 3-Methyl-l-(vinyloxy)-butane-R_x 79. 4-Methylpentanal-R_x 80. Furan-2-carbaldehyde-R_x 81. (E)-2-Hexenal-R_x 82. (E)-4-oxo-2-Hexenal-R_x 83. (E,E)-2,4-Dimethyl-2,4-hexadienal-R_x 84. (E,E)-2,4-Hexadienal-R_x 85. (Z)-2-Hexenal-R_x 86. (Z)-3-Hexenal-R_x 87. (Z)-4-oxo-2-Hexenal-R_x 88. 1-Hexenal-R_x 89. 2,3-Dihydrox ybenzaldeh yde-R_x 90. 2-Hexenal-R_x 91. 3-((E)-2-Hexenoxy)-hexanal-R_x 92. 3,5 -Dimethy lhex anal-R_x 93. 3-Ethoxyhexanal-R_x 94. 3-H ydroxybenzaldeh yde-R_x 95. 3-Hydroxyhexanal-R_x 96. 4- Hydroxy-3,5 -dimethox ybenzaldeh yde- R_x 97. 4-Hydroxybenzaldehyde-R_x 98. 5-Methylhexanal-R_x 99. Hexanal-R_x 100. (1R,2S,5S)-Iridodial-R_x 101. (lR,5S)-6,6-Dimethylbicyclo[3.1.1]hept-2-ene-2-carbaldehyde-R_x 102. (IS, 2 R,3S )-2-(1 -Form ylviny 1)-5 -methylcyclopentanecarbaldehyde-R_x 103. (3S,8R)-2-Methyl-5-( 1 -formylethyl)-1-cyclopentene-1 -carbaldehyde-R_x

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104. (3 S,8 S )-2-Methy 1-5-( 1-formylethy 1)-1-eye lopentene-l-carbaldehyde-R_x 105. {5S,8S)-2-Methyl-5-( 1 -formylethyl)-1 -cyclopentene-1 -carbaldehyde-R_x 106. (E)-2-(2-Hydroxyethyl )-6-methy 1-2,5-heptadienal-R_x 107. (E)-2-(2-Hydroxyethylidene)-6-methyl-5-heptenal-R_x 108. (E)-2-Heptenal-R_x 109. (E)-2-Isopropyl-5 -meth y 1 -2-hexenal- R_x 110. (E,Z)-2,4-Heptadienal-R_x 111. (R)-2-(( 1 R,2R,3S)-3-Methyl-2-vinylcyclopentyl)-propanal-R_x 112. (R)-2-(( 1 S,2S,3S)-3-Methyl-2-vinylcyclopentyl)-propanal-R_x 113. (R)-2,6-Di methyl-5-heptenal-R_x 114. (R)-7-Hydroxy-6,7-dihydro-5H-pyiTolizidine-l-carboxaldehyde-R_x 115. (S)-4-(Prop-1 -en-2-yl)-cyclohex-1 -enecarbaldehyde-R_x 116. {S)-7-Hydroxy-6,7-dihydiO-5H-pyrrolizidine-!-carboxaldehyde-R_x 117. (Z)-2-IsopiOpyl-5-methyl -2-hexenal -R_x 118. 1-Formyl-6,7-dihydro-5H-pyiTolizine-R_x 119. 1 -Formyl-7 -hydroxy-6,7-dihydro-5H-pyrrolizine-R_x 120. 2-(3-Methylcyclopenty])-propanal-R_x 121. 2,6-Dimethyl-5-beptenal-R_x 122. 2-Acetyl-5-methylcyclopentanecarbaldehyde-R_x 123. 2-Methoxybenzaldehyde-R_x 124. 2-Methyl-1 -cyclopentenecaj'boxaldehyde-R_x 125. 3,3-Dimethyl-5-oxo-7-oxabjcyclo[4.1,0]heptane-1 -carba)dehyde-R_x 126. 3-Hydroxybenzene-1,2-dicarbaldehyde-R_x 127. 3-Methylbenzaldehyde-R_x 128. 4-(Heptyloxy)-butanal-R_x 129. 4-Methoxybenzaldehyde-R_x 130. 6,7-Dihydro-5H-pyrrolizine-l-carboxaldehyde-R_x 131. 6,7-Dihydro-7-oxo-5H-pyrrolizine-l-carbaldebyde-R_x 132. 6-Methylheptanal-R_x 133. 7-Hydroxy-6,7-dihydro-5 H-pyrroli zin-1 -carboxal dehyde-R_x 134. Benzaldehyde-R_x 135. Cyclohexanedial-R_x 136. Heptanal-R_x 137. Plaaiodial-R_x 138. (lR,2S)-cis-2-Isopropenyl-l-methylcyclobutaneethanal-R_x 139. (1 R,2S,5R,8R)-Iridodial-R_x 140. (4S)-(3-Oxoprop- l-en-2-yl)-cyclohex-l-enecai^-baldehyde-R_x 141. (E)-2-(3,3-Di methy icyc 1 ohexylidene)-acetaldehyde- R_x 142. (E)-2-(4-Methyl-3-pentenyl)-butenedial-R_x 143. (E)-2-(4-Meth yl-3-pentenylidene)-butanedial-R_x 144. (E)-2,7-Octadienal-R_x 145. {E)-2-Methyl-5-(3-furyl)-2-pentenal-R_x 146. (E)-2-Octenal-R_x 147. (E)-3,7-Dimethyl-2,6-octadienal-R_x

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148. (E)-3,7-Dimethyl-2,6-octadienal-R_x 149. (E)-4-oxo-2-Octenal-R_x 150. (E)-7-Methyl-2-octenal-R_x 151. (E,E)-2,4-Octadienal-R_x 152. (E,E)-2,6-Dimethyl-8-hydroxy-2,6-octadienal-R_x 153. (E,E)-2,6-Octadienal-R_x 154. (E,E)-2,6-Octadienedial-R_x 155. (E,Z)-2,4-Octadienal-R_x 156. (E,Z)-2,6-Octadienal-R_x 157. (Z)-2-( 3,3-Dimeth y Icyclohexy lidene)-acetaldehyde-R_x 158. (Z)-3,7-Dimethyl-2,6-octadienal-R_x 159. (Z,E)-3,7-Dimethyl-2,6-octadiena1-R_x 160. 1-Octenal-R_x 161. 2-(1 -Formyl vinyl)-5-methylcyc!opentanecarbaldehyde-R_x 162. 2,6,6-Trimethyl-l-cyclobexene-l-carbaIdehyde-R_x 163. 2-Ethyloctanal-R_x 164. 2-H ydroxy-6- meth y Ibenzaldeh yde-R_x 165. 2-Meth yl benzaldehyde-R_x 166. 2-Octenal-R_x 167. 2-Phen ylpro penal-R_x 168. 3,7-Dimethyl-6-octenal-R_x 169. 3-Ethoxy-4-hydroxybenzaldehyde-R_x 170. 3-Ethyl benzaldehyde-R_x 171. 3-Isopropyl-6-methyl benzaldehyde-R_x 172. 3-Octenal-R_x 173. 3-o xo-4-Isopropyl idene-1 -cyclohexene-1 -carboxya1dehyde-R_x 174. 4-Hydroxy-2-methyl benzaldehyde-R_x 175. 4-Hydroxy-3-methoxybenzaldehyde-R_x 176. 4-Isopropenyl-1 -cyclohexene-1 -carbaldehyde-R_x 177. 4-Isopropenyl-3-oxo-l-cyclohexene-l-carboxyaldehyde-R_x 178. 4-oxo-Octenal-R_x 179. 4S-4-Isopropenyl-3-oxo-1 -cyclohexene-1 -carboxyaldehyde-R_x 180. 6,6-Dimethylbicyclo[3.1. l]hept-2-ene-2-carbaldehyde-R_x 181. 7-Methyloctanal-R_x 182. Anisomorphal-R_x 183. cis-2-Isopropenyl-1 ~methylcyclobutaneethanal~R_x 184. Octanal-R_x 185. PerLiphasmal-R_x 186. (E)-4,8-Nonadienal-R_x 187. (E)-8-Methyl-2-nonenal-R_x 188. (E,E)-2,4-N onadienal-R_x 189. (E,E,E)-2,4,6-Nonatrienal-R_x 190. (E,E,Z)-2,4,6-Nonatrienal-R_x 191. (E,Z)-2,6-Nonadienal-R_x

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192. (E,Z,Z)-2,4,6-Nonatnenal-R_x 193. {Z)-3-Nonenal-R_x 194. (Z)-4,8-Nonadienal-R_x 195. (Z)-4-Nonenal-R_x 196. (Z)-8-Methyl-2-nonenal-R_x 197. 2-Phenyl-2-butenal-R_x 198. 3-(4- Methoxyphenyl )-2-propenal-R_x 199. 3-Phen yl -2-propenal-R_x 200. 3-Phenylpropanal-R_x 201. 6-Ethyl benzaldehyde-R_x 202. 8-Methylnonanal-R_x 203. 9-Acetyloxynonanal-R_x 204. Nonanal-R_x 205. (E)-2,9-Decadienal-R_x 206. (E)-2-Decenal-R, 207. (E)-4-oxo-2-Decenal-R_x 208. (E)-8-Hydroxy-4,8-d imethyl-4,9-decadienal-R_x 209. (E)-9-Methyl-2-decenal-R_x 210. (E,E)-2,4-Decadienal-R_x 211. (E,Z)-2,4-Decadienal-R_x 212. (Z)-4- Decenal-R_x 213. (Z)-5-Decenal-R_x 214. (Z)-9-Methyl-2-decenal-R_x 215. 1-Decenal-R_x 216. 2-Decenal-R_x 217. 2-Ethyldecanal-R_x 218. Decanal-R_x 219. (5E)-2,6,10-Trimethylundeca-5,9-dienal-R_x 220. (E)-2-Undecenal-R_x 221. (E)-6-Ethyl-2,10-dimethyl-5,9-undecadienal-R_x 222. 10-Undecenal-Rx 223. 2-Butyl-2-octenal-R_x 224. 5-Methyl-2-phenyl-2-hexenal-R_x 225. 8-Iso propyl-5 -meth y 1-3,4,4a,5,6,7,8,8a-octah ydronaphthalene-2-carbaldehyde-R_x 226. syn-4,6-Dimethylundecanal-R_x 227. Undecanal-R_x 228. (3R,5 R,9R )-3,5,9-Tri meth yldodecanal-R_x 229. (3S,6E)-7-Ethyl-3,l l-dimethyldodeca-6,10-dienal-R_x 230. (9R)-3,5,9-T rimethy ldodecanal-R_x 231. (E)-10-Dodecenal-R_x 232. (E)-2-Dodecenal-R_x 233. (E)-3,7,11 -Trimethyl-6,10-dodecadienal-R_x 234. (E)-6- Dodecenal-R_x 235. (E)-7-Dodecenal-R_x

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236. (E)-8-Dodecenal-R_x 237. {E)-9,l 1-Dodecadjenal-R_x 238. (E)-9-Dodecenal-R_x 239. (E,E)-3,7,1 l-Trimethyl-2,6,10-dodecatrienal-R_x 240. (E,E)-7-Ethyl-3,1 1-dimethyl-2,6,10-dodecatrienal-R_x 241. (E,E )-8,10-Dodecadienal-R_x 242. (E,E,E)-3,7-Dimethyl-8,11 -dioxo-2,6,9-dodecatrienal-R_x 243. (E,E,Z)-3,7-Dimethyl-8,11 -dioxo-2,6,9-dodecatrienal-R_x 244. (E,Z)-5,7-Dodecadienal- R_x 245. (E,Z)-7,9-Dodecadienal-R_x 246. (E,Z)-8,10-Dodecadienal-R_x 247. (S,E)-3,7,1 l-Trimethyl-6,10-dodecadienal-R_x 248. {Z)-2-Methy1-5-((lR,5R,6S)-2,6-dirnethy1bicyclo[3.1,I]hept-2-en-6-yl)-pent-2-enal-R_x 249. (Z)-5-Dodecenal-R_x 250. (Z)-7-Dodecenal-R_x 251. (Z)-9,l 1-Dodecadienal-R_x 252. (Z)-9-Dodecenal-R_x 253. (Z,E)-3,7,! 1-Trimethyl-2,6,10-dodecatrienal-R_x 254. (Z,E)-5,7- Dodecadienal -R_x 255. (Z,E)-7-Ethyl-3,1 l-dimethyl-2,6,10-dodecatrienal-R_x 256. (Z,E)-8,10-Dodecadienal-R_x 257. (Z,Z)-5,7-Dodecadienal-R_x 258. 2~Ethyldodecanal-R_x 259. 3,7,11 -Trimethyl-(E)-6,10-dodecadienal-R_x 260. Dodecanal-R_x 261. syn-4,6-Di methyldod ecanal-R_x 262. (3S,4R,6E, 10Z)-3,4,7,11 -Tetramethyl-6,10-tridecadienal-R_x 263. (Z)-4-Tridecenal-R_x 264. 13-Acetyloxytridecanal-R_x 265. Tridecanal-R_x 266. (E)-l l,13-Tetradecadienal-R_x 267. (E,E)-8,10-Tetradecadienal-R_x 268. (E,Z)-4,9-Tetradecadienal-R_x 269. (Z)-l l,13-Tetradecadienal-R_x 270. (Z)-5-Tetradecenal-R_x 271. (Z)-7-Tetradecenal-R_x 272. (Z)-9,13-Tetradecadien-11 -ynal-R_x 273. (Z,E)-9,12-Tetradecadienal-R_x 274. (Z,Z)-8,10-Tetradecadienal-R_x 275. (Z,Z)-9,11-Tetradecadienal-R_x 276. i 0,12-Tetradecadienal-Rx 277. 2-Ethyltetradecanal-R_x 278. 3-oxo-13-Tetradecenal-R_x 279. 3-oxo-Tetradecanal-R_x

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280. 5,8-Tetradecadienal-R_x 281. 5-Tetradecenal-R_x 282. (E)-5,9-Dimethyl-2-(6-methylhept-5-en-2-yl)-deca-4,8-dienal-R_x 283. (E,Z)-9,I1-Pentadecadienal-R_x 284. (Z)-1O-Pentadecenal-R_x 285. (Z)-6,14-Pentadecadienal-R_x 286. (Z,Z)-9,11-Pentadecadienal-R_x 287. 2-Hexyl-2-decenaER_x 288. Pentadecanal-R_x 289. (lR)-Pimaral-Rx 290. (E)- 10-Hexadecenal-R_x 291. (E)-i 1-Hexadecenal-R_x 292, {E,E)-10,14- Hexadecadienal- R_x 293. (E,E)-1 l,13-Hexadecadienal-R_x 294. (E,E)-9,11-Hexadecadienal-R_x 295. (Ε,Ε,Ε)-10,12,14-Hexadecatrienal-R_x 296. (E,E,E)-3,7,1 l,15-teti-amethyl-2,6,10,14-hexadecatetraenal-R_x 297. (Ε,Ε,Ζ)-10,12,14-Hexadecatrienal-R_x 298. (E,E,Z)-4,6,11 -Hexadecatriertal-R_x 299. (Ε,Ε,Ζ,Z)-4,6,1 l,13-Hexadecatetraenal-R_x 300. (E,Z)-10,12-Hexadecadienal· R_x 301. (E,Z)-1 l,13-Hexadecadienal-R_x 302. (E,Z)-4,6-Hexadecadienal-R_x 303. (E,Z)-6,11-Hexadecadienal-R_x 304. (E,Z)-8,11-Hexadecadienal-R_x 305. (E,Z)-9,11 - Hexadecadienal-R_x 306. (Z)-10-Hexadecenal-R_x 307. (Z)- 12-Hexadecenal-R_x 308. (Z)-13-Hexadecen-1 l-ynal-R_x 309. (Z)-3-oxo-9-Hexadecenal-R_x 310. (Z,E)-10,12-Hexadecadienal-R_x 311. (Z,E)-11,13-Hexadecadie nal-R_x 312. (Z,E)-7,11-Hexadecadienal-R_x 313. (Z,E)-9,11-Hexadecadienal-R_x 314. (Z,Z)-10,12-Hexadecadienal-R_x 315. (Z,Z)-1l,13-Hexadecadienal-R_x 316. (Z,Z)-9,11 - Hexadecadienal- 317. 11-Hexadecynal-R_x 318. 2-Methylhexadecanal-R_x 319. 7-Hexadecenal-R_x 320. 9-Hexadecenal-R_x 321. (Z)-9-Heptadecenal-R_x 322. 1-Heptadecenal-R_x 323. 2-1leptadecenal-R,

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324. Heptadecanal-Rx 325. {E)-l l-Octadecenal-Rx 326. (E)-13-Octadecenal-R_x 327. (E)-14-Octadecenal-R_x 328. (E)-2-Octadecenal-R_x 329. (E,E)-11,14-Octadecadienal-R_x 330. (E,Z)-2,13-Octadecadienal-R_x 331. (E,Z)-3,13-Octadecadienal-Rx 332. (Z)-11 -Octadecenal-R_x 333. (Z)-13-()ctadecenal-IT 334. (Z)-9-Octadecenal-R_x 335. (Z,Z)-11,13-Octadecadienal-R_x 336. (Z,Z)-13,15-Octadecadienal-R_x 337. (Z,Z)-3,13-Octadecadienal-R_x 338. (Z,Z)-9, i 2-Octadecadienal-R_x 339. (Z,Z,Z)-9,12,15-Octadecatrienal-R_x 340. 1 -Octadecenal-R_x 341. 9-OctadecenaER_x 342. Octadecanal-R_x 343. (Z)-10-Nonadecenal-R_x 344. (Z)-9-Nonadecenal-R_x 345. (Z)-l 1-Eicosenal-R_x 346. 12-Deacetoxy-12-oxo-scalaradial-R_x 347. 1-Eicosenal-R_x 348. Deacetylscalaradial-R_x 349. Eicosanal-R_x 350. Scalaradial-R_x 351. Docosanal-R_x 352. Tetracosanal-R_x 353. Pentacosanal-R_x 354. Hexacosanal-R_x 355. Heptacosanal-R_x 356. Octacosanal-R_x 357. Triacontanal-R_x 358. Dotriacontanal-R_x

4. The composition according to one of Claims 1-3, wherein the deuterium-enriched aldehyde is a pheromone and the composition is useful for modulating the behavior of insects.

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5. The composition according to Claim 4, further comprising: an optional additional component suitable for the composition, the component being selected from: a pesticide, solvent, dispensing material or device, and an adhesive capable of trapping an insect.
6. The composition according to one of Claims 1-5, wherein the deuterium isotope in R_x is in an amount greater than 50 percent of the hydrogen atoms present in R_x.
7. The composition according to one of Claims 1-5, wherein the deuterium isotope in R_x is in an amount greater than 90 percent of the hydrogen atoms present in R_x.
8. A method of modulating the behavior of insects, comprising: introducing a modulating composition to an area to be protected from the insects, the modulating composition, comprising a deuterium-enriched aldehyde of Claim 1.
9. The method of claim 8, wherein the deuterium-enriched aldehyde pheromone is selected from an aldehyde of Claim 2,
10. The method of claim 8, wherein the deuterium-enriched aldehyde pheromone is selected from an aldehyde of Claim 3.
11. The method according to one of Claims 8-10, wherein modulation, comprises: attracting an insect to a trap.

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12. The method according to one of Claims 8-10. wherein modulation, comprises: disruptin insect mating.
13. The method according to one of Claims 8-12, wherein the deuterium isotope in R_x is in an amount greater than 50 percent of the hydrogen atoms present in R_x.
14. The method according to one of Claims 8-12, wherein the deuterium isotope in R_x is in an amount greater than 90 percent of the hydrogen atoms present in R_x,
15. The method according to one of Claims 8-14, wherein the method further comprises: applying the pheromone to a surface of a trap wherein the insect enters but cannot leave,

16. The method according to one of Claims 8-14, wherein introducing, comprises:

distributing the pheromone into the area to be protected, wherein the pheromone disrupts insect mating and is distributed impregnated on a chip, in a polymer hollow fiber, or adsorbed in a lubber septum.

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OO o

<N

IT) <N

O oo o

<N oo o

<N

Air Oxidation of Benzaldehyde to Benzoic Acid

100% 90% fl ‘5 80% '5 a Φ 70% tt i> 60% •ϋ >> Λ Φ 50% 2 2 40%; N fl Φ 30%· S3 20% 10%· ()%

-φ......w

12 15

Time (hours)

SBenzaldehyde-D Renzaldehyde-I I

Figure 1

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Air Oxidation of Hexanal to Hexanoic Acid

0 3 6 9 12 15 18 21 24

Time (hours)

0 3 6 9 12 15 18 21 24

Time (hours)

Tl Iexanal-11 sgl lexanal-D

Figure 2